Microbial transformation of ethylpyridines

Pyridine and its derivatives have been found as pollutants in the environment. Although alkylpyridines constitute the largest class of pyridines contaminating the environment, little information is available concerning the fate and transformation of these compounds. In this investigation ethylpyridines have been used as model compounds for investigating the biodegradability of alkylpyridines. A mixed culture of ethylpyridine-degrading microorganisms was obtained from a soil that had been exposed to a variety of pyridine derivatives for several decades. The enrichment culture was able to degrade 2-, 3-, and 4-ethylpyridine (100 mg/L) at 28° C and pH 7 within two weeks under aerobic conditions. The degradation rate was greatest for 2-ethylpyridine and least for 3-ethylpyridine. Transformation of ethylpyridines was dependent on substrate concentration, pH, and incubation temperature. Studies on the metabolic pathway of 4-ethylpyridine revealed two products; these chemicals were identified by MS and NMR analyses as 4-ethyl-2(1H)-pyridone and 4-ethyl-2-piperidone. 6-Ethyl-2(1H)-pyridone was determined to be a product of 2-ethylpyridine degradation. These results indicate that the transformation mechanism of ethylpyridines involves hydroxylation and reduction of the aromatic ring before ring cleavage.     

Spin Trapping of Methyl Radicals by the Acyl Nitroso Compound PH-C (= O)NO Formed in the Photochemical Reaction Between Benzohydroxamic Acid, Dimethyl Sulfoxide and Hydrogen Peroxide. An Epr Study

By the use of EPR spectroscopy, it has been shown that acyl nitroso compounds can act as spin traps for short-lived radicals with the formation of acyl aminoxyl radicals. The reaction was studied for the system benzohydroxamicacid[Ph-C (= O)N(H)] - dimethyl sulfoxide - hydrogen peroxide. The acyl aminoxyl radicals appeared almost immediately when the reaction mixture was irradiated in situ in the EPR cavity with UV light. The trapping reaction involved two photochemical reactions, i.e. the oxidation of the hydroxamic acid to the acyl nitroso compound Ph-C (= O)NO, and the formation of methyl radicals from dimethyl sulfoxide. The EPR spectra are superpositions of the spectra of two species of acyl aminoxyl radicals, i.e. the radicals Ph-C (= O)N(O·)H formed by oxidation of the parent benzohydrox-amic acid, and the radical Ph-C (= O)N(O·)CH₃, formed by trapping of methyl radicals.     

Ontogenetic patterns of volatiles identified in Dufour's gland extracts from queens and workers of the primitively eusocial halictine bee,Lasioglossum malachmum (Hymenoptera: Halictidae)

Summary Ontogenetic patterns of volatile compounds identified in Dufour's gland extracts from queens and workers of the primitively eusocial sweat beeLasioglossum malachurum (K.) were compared. Only young unmated queens showed high proportions of isopentenyl esters, while macrocyclic lactones were dominant in old breeding queens, spring queens, and workers. In young queens the relative and absolute amounts of volatiles changed one day after mating. A discriminant analysis revealed significant differences in odor patterns of unmated and mated young queens. The fat body was the largest in young females, while eggs could be recorded only in breeding queens. Possible functions of different odor components in the investigated female groups are discussed.     

INTRACELLULAR LOCALIZATION OF THE TASTE/ODOR METABOLITE 2-METHYLISOBORNEOL IN OSCILLATORIA LIMOSA (CYANOPHYTA)1

The monoterpene derivative, 2-methylisoborneol (MIB), is produced by many blue-green algae and often is responsible for the “musty” taste/odor in aquaculturally raised finfish and potable water supplies. Although previous researchers have suggested that taste/odor metabolites are partitioned among cell constituents and that coregulation with pigment biosynthesis occurs, no structural evidence for these hypotheses exists. MIB was localized in cells of Oscillatoria limosa (Roth) Agardh at the ultrastructural level using standard gold-labeled antibody techniques. There was no apparent relationship between age of the cells and MIB synthesis; cells that were and were not undergoing active division had similar amounts of MIB label. There was no consistent partitioning of MIB label within cells. However, occasionally, specific label was observed along photosynthetic lamellae, suggesting a potential linkage of MIB synthesis and/or binding to the pigment systems.     

Bio-availability of phosphorus in sediments of the western Dutch Wadden Sea

The purpose of this study was to make a prognosis of the effects of extended purification of terrestrial waste water, reaching the Wadden Sea by the River Rhine and Lake IJssel, on the phosphate concentration in the western Wadden Sea.The quantities of different phosphorus fractions in intertidal and subtidal sediments of the Marsdiep tidal basin (western Dutch Wadden Sea) were measured. Different methods are applied to determine the amount of phosphorus that can be released from these sediments. The direct bioavailability is determined by inoculating sediment suspensions with a natural mixture of precultured micro-organisms from the sampling area. A second approach is the measurement of the phosphate release under different redox conditions. Sequential extraction of sediment samples with different solvents is also applied. Under the present conditions and compared to the nutrient loads from fresh water (Lake IJssel) and from the North Sea, the phosphorus stored in the sediments of the western Dutch Wadden Sea plays a minor role in the total supply to micro-algae and bacteria. The bulk of the biologically available phosphorus in the sediments originates from the metal-associated fraction. Releasable phosphate may contribute to the local annual primary production to an extent of ca 45 to ca 150 g C m^–2 a^–1. The total amount of phosphorus in the sediment (mainly calcite associated) is twice to 6 times the biologically available amount.     

Anaerobic degradation of dimethylsulfoniopropionate to 3-S-methylmercaptopropionate by a marine Desulfobacterium strain

Dimethylsulfoniopropionate, an osmolyte of marine algae, is thought to be the major precursor of dimethyl sulfide, which plays a dominant role in biogenic sulfur emission. The marine sulfate-reducing bacterium Desulfobacterium strain PM4 was found to degrade dimethylsulfoniopropionate to 3-S-methylmercaptopropionate. The oxidation of one of the methyl groups of dimethylsulfoniopropionate was coupled to the reduction of sulfate; this process is similar to the degradation betaine to dimethylglycine which was described earlier for the same strain. Desulfobacterium PM4 is the first example of an anaerobic marine bacterium that is able to demethylate dimethylsulfoniopropionate.Abbreviations DMSP dimethylsulfoniopropionate - DMS dimethyl sulfide - MMPA 3-S-methylmercaptopropionate     

Demethylation and degradation of phenylmethylethers by the sulfide-methylating homoacetogenic bacterium strain TMBS 4

Biochemical studies on anaerobic phenylme-thylether cleavage by homoacetogenic bacteria have been hampered so far by the complexity of the reaction chain involving methyl transfer to acetyl-CoA synthase and subsequent methyl group carbonylation to acetyl-CoA. Strain TMBS 4 differs from other demethylating homoacetogenic bacteria in using sulfide as a methyl acceptor, thereby forming methanethiol and dimethylsulfide. Growing and resting cells of strain TMBS 4 used alternatitively CO₂ as a precursor of the methyl acceptor CO for homoacetogenic acetate formation. Demethylation was inhibited by propyl iodide and reactivated by light, indicating involvement of a corrinoid-dependent methyltransferase. Strain TMBS 4 contained ca. 750 nmol g dry mass^-1 of a corrinoid tentatively identified as 5-hydroxybenzimidazolyl cobamide. A photometric assay for measuring the demethylation activity in cell extracts was developed based on the formation of a yellow complex of Ti³⁺ with 5-hydroxyvanillate produced from syringate by demethylation. In cell extracts, the methyltransfer reaction from methoxylated aromatic compounds to sulfide or methanethiol depended on reductive activation by Ti³⁺. ATP and Mg²⁺ together greatly stimulated this reductive activation without being necessary for the demethylation reaction itself. The specific activity of the transmethylating enzyme system increased proportionally with protein concentration up to 3 mg ml^-1 reaching a constant level of 20 nmol min^-1 mg^-1 at protein concentrations 10 mg ml^-1. The specific rate of activation increased in a non-linear manner with protein concentration. Strain TMBS 4 degraded gallate, the product of sequential demethylations, to 3 acetate through the phloroglucinol pathway as found earlier with Pelobacter acidigallici.Abbreviations BV benzyl viologen - CTAB cetyltrimethylammonium bromide - H₄folate tetrahydrofolate - MOPS 3-[N-morpholino]propanesulfonic acid - MV methyl viologen - NTA nitrilotriacetate - t_d doubling time - TMB 3,4,5-trimethoxybenzoate     

Effect of Organic Acids on Reactions Catalyzed by Manganese Peroxidase from Phanerochaete chrysosporium

The effect of several organic acids on the oxidation of Mn(II) catalyzed by manganese peroxidase was studied. Reactivities of manganese peroxidase and chemically prepared Mn(III) organic acid complexes towards phenolic compounds were compared. If lactate appears to be the best complexant for manganese peroxidase activity, chemically prepared Mn(III)—lactate complex is a less effective oxidant towards phenolic compounds than other Mn(III)—complexes. Our results agree with the hypothesis that certain organic acids are involved in the catalytic cycle of manganese peroxidase. Malonate and lactate seem to be the most attractive complexants for practical applications of manganese peroxidase and were used in enzymatic treatment of hardwood kraft pulp. Bleaching of kraft pulp was studied and after alkaline extraction, a significant decrease of kappa number was measured. The bleaching was enhanced in lactate buffer.     

Multistimuli-responsive fluorescence behaviours of aggregation-induced emission small-molecule and electrospun nanofibre films for acid–base vapour sensing

Multistimuli-responsive fluorescent materials have garnered great research interest benefited from their practical applications. Two twisted-structure compounds containing tetraphenylethylene (TPE) as the aggregation-induced emission (AIE) group and a pyridine unit as the acid reaction site to obtain new multistimuli-responsive fluorescent compounds (namely, TPECNPy: TPECNPy-2 and TPECNPy-3) were successfully synthesized through a one-step Knoevenagel condensation reaction. The multiple-stimuli response process of TPECNPy was investigated by means of photoluminescence (PL) spectra and emission colour. The results showed that both TPECNPy compounds with excellent AIE abilities displayed reversible emission wavelength and colour changes in response to multiple external stimuli, including grinding–fuming by CH₂Cl₂ or annealing and HCl-NH₃ vapour fuming. More importantly, fluorescent nanofibre films were prepared by electrospinning a solution of TPECNPy mixed with cellulose acetate (CA), and these exhibited reversible acid-induced discolouration, even with only 1 wt% TPECNPy. The results of this study may inspire strategies for designing multistimuli-responsive materials and preparing fluorescent sensing nanofibre films.     

细菌吸附及转运芳香族化合物的研究进展

芳香族化合物是一类具有苯环结构的有机物,它们结构稳定,不易分解,并可通过食物链进行生物富集和生物放大,对生态环境及人类健康造成极大危害。细菌具有超强的分解代谢能力,能降解多环芳烃(polycyclic aromatic hydrocarbons, PAHs)等多种难降解芳香族污染物。吸附和转运是细菌进行芳香族化合物细胞内代谢的前提。虽然芳香族化合物的细菌降解已取得较为显著的研究进展,但吸附和转运机理仍不甚清楚。本文讨论了细菌对芳香族化合物的吸附有积极作用的细胞表面疏水性、生物被膜形成和细菌趋化性等影响因素,总结了FadL家族、TonB依赖性受体蛋白、OmpW家族等外膜转运系统和主要协同转运蛋白超家族(major facilitator superfamily, MFS)转运体、ATP结合盒(ATP-binding cassette, ABC)转运蛋白等内膜转运系统对该类化合物跨膜运输作用,并对跨膜转运机制进行了讨论和阐述,旨在为芳香族污染物的防控和治理提供一定理论参考。