Microbial Reduction of Lepidocrocite γ-FeOOH by Shewanella putrefaciens; The Formation of Green Rust

Dissimilatory iron-reducing bacteria (DIRB) couple the oxidation of organic matter or H₂ to the reduction of iron oxides. The bacterial reduction of a most common well-crystallised ferric oxyhydroxide, -FeOOH was investigated using DIRB Shewanella putrefaciens, strain CIP 8040. Experiments were conducted in the presence of neither organic buffer nor phosphate, with formate as electron donor, bicarbonate, and anthraquinone-2,6-disulfonate (AQDS, a humic acid analogue) that influenced the extent of ferric oxide bioreduction. The production of Fe²⁺ was followed with time. The solid phases obtained after bacterial iron reduction were analysed by transmission Mössbauer spectroscopy (TMS) and X-ray diffraction (XRD). Biogenic formation of green rust 1 compound, which contains carbonate anions, [Fe^II ₂Fe^III ₂(OH)₈]²⁺[CO₃ ^2–]^2– was observed. TMS was used to follow the evolution of the green rust abundance during the bacterial culture.     

Isomeric hexyl‐ketohydroperoxides formed by reactions of hexoxy and hexylperoxy radicals in oxygen

Isomerization reactions of peroxy radicals during oxidation of long‐chain hydrocarbons yield hydroperoxides, and therefore play an important role in combustion and atmospheric chemistry, because of their action as branching agents in these chain reaction processes. Different formation mechanisms and structures are involved. Three isomeric hexyl‐ketohydroperoxides are formed via isomerization reactions in oxygen of either hexoxy RO or hexylperoxy RO₂ radicals. In the temperature range 373–473 K, 2‐hexoxy (C₆H₁₃O) radical in O₂/N₂ mixtures gives 2‐hexanone‐5‐hydroperoxide via two consecutive isomerizations. The second one is a H transfer from a HC(OH) group occurring via a seven‐membered ring intermediate: Its rate constant has been determined at 453 and 483 K, and the general expression can be written as Hexylperoxy C₆H₁₃O₂ radical, present in n‐hexane oxidation by oxygen/nitrogen mixtures in the temperature range 543–573 K, gives 2‐hexanone‐4‐hydroperoxide, 3‐hexanone‐5‐hydroperoxide, and 2‐hexanone‐5‐hydroperoxide. The first two are formed through an isomerization reaction via a six‐membered ring intermediate, and the last through an isomerization reaction via a seven‐membered ring intermediate. The ratio of the rate constant of the isomerization reactions of RO₂ radicals via a seven‐membered ring intermediate to that via a six‐membered ring is found to be 0.795, and the rate constant expression via a seven‐membered ring intermediate is proposed: The role of these reactions in the formation of radicals in the troposphere is discussed. Other products arising in the reactional path, such as ketones, furans, and diketones, are identified. Identification of these ketohydroperoxides was made using gas chromatography/mass spectrometry with electron impact, and with NH₃ (or ND₃) chemical ionization. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 354–366, 2003     

Monitoring structural transformation of hydroxy-sulphate green rust in the presence of sulphate reducing bacteria

The activities of bacterial consortia enable organisms to maximize their metabolic capabilities. This article assesses the synergetic relationship between iron reducing bacteria (IRB), Shewanella putrefaciens and sulphate reducing bacteria (SRB) Desulfovibrio alaskensis. Thus, the aim of this study was first to form a biogenic hydroxy-sulpahte green rust GR2( $ {\text{SO}}_{{\text{4}}} ^{{2 - }} The activities of bacterial consortia enable organisms to maximize their metabolic capabilities. This article assesses the synergetic relationship between iron reducing bacteria (IRB), Shewanella putrefaciens and sulphate reducing bacteria (SRB) Desulfovibrio alaskensis. Thus, the aim of this study was first to form a biogenic hydroxy-sulpahte green rust GR2() through the bioreduction of lepidocrocite by S. putrefaciens and secondly to investigate if sulfate anions intercalated in the biogenic GR2() could serve as final electron acceptor for a sulfate reducing bacterium, D. alaskensis. The results indicate that the IRB lead to the formation of GR2() and this mineral serve as an electron acceptor for SRB. GR2() precipitation and its transformation was demonstrated by using X-ray diffraction (DRX), M?ssbauer spectroscopy (TMS) and transmission electron spectroscopy (TEM). These observations point out the possible acceleration of steel corrosion in marine environment in presence of IRB/SRB consortia.     

Decomposition of Acetaldehyde in Atmospheric Pressure Filamentary Nitrogen Plasma

The removal of 500?ppm acetaldehyde in nitrogen at 1?bar is characterized in a pulse dielectric barrier discharge generating a spatial random distribution of plasma filaments. The identification and the quantification of numerous by-products are performed. At 20?°C, CH₃CHO is efficiently dissociated, probably owing to quenching of N₂ metastable states. The most abundant by-products are CO, H₂, and CH₄, in consistency with the three important exit channels for the quenching of the N₂(A³?? _u ⁺ ) state by CH₃CHO proposed by Faider et al. (2011). In order of importance, other products are HCN, C₂H₆, CH₃CN, HNCO, CO₂, CH₃COCH₃, C₂H₄, C₂H₅CN, NH₃, C₂H₂, and a group of nitriles and of ketones. An increase of the temperature from 20?°C up to 300?°C induces a strong decrease of the removal characteristic energy, but the by-products types remain unchanged. Probably the reaction of H with CH₃CHO plays a role in the removal of the molecule at 300?°C.     

Plasma Reactivity and Plasma-Surface Interactions During Treatment of Toluene by a Dielectric Barrier Discharge

Toluene removal is investigated in filamentary plasmas produced in N₂ and in N₂/O₂ mixtures by a pulse high voltage energised DBD. Influence of the oxygen percentage (lower than 10%) and of the temperature (lower than 350°C) is examined. Toluene is removed in N₂ through collisions with electrons and nitrogen excited states. The removal efficiency is a few higher in N₂/O₂. It increases when the temperature increases for N₂ and N₂/O₂. Both H- and O-atoms play an important role in toluene removal because H can readily recombine with O to form OH, which is much more reactive with toluene than O. H follows from dissociation of toluene and of hydrogenated by-products by electron collisions. Detection of cyanhidric acid, acetylene, formaldehyde, and methyl nitrate strengthens that dissociation processes, to produce H and CH₃, must be taken into account in kinetic analysis. Formation and treatment of deposits are also analysed.     

Multiscale dynamics of the cell envelope of Shewanella putrefaciens as a response to pH change

The bacterial surface properties of gram-negative Shewanella putrefaciens were characterized by microbial adhesion to hydrocarbons (MATH), adhesion to polystyrene dishes, and electrophoresis at different values of pH and ionic strength. The bacterial adhesion to these two apolar substrates shows significant variations according to pH and ionic strength. Such behavior could be partly explained by electrostatic repulsions between bacteria and the solid or liquid interface. However, a similar trend was also observed at rather high ionic strength where electrostatic interactions are supposed to be screened. The nanomechanical properties at pH 4 and 10 and at high ionic strength were investigated by using atomic force microscopy (AFM). The indentation curves revealed the presence of a polymeric external layer that swells and softens up with increasing pH. This suggests a concomitant increase of the water permeability and so did of the hydrophilicity of the bacterial surface. Such evolution of the bacterial envelope in response to changes in pH brings new insight to the pH dependence in the bacterial adhesion tests. It especially demonstrates the necessity to consider the hydrophobic/hydrophilic surface properties of bacteria as not univocal for the various experimental conditions investigated.     

Probing the modifications of polystyrene surface properties after incubation with the Shewanella putrefaciens bacteria at two pH values (4, 10) by atomic force microscopy

The local surface properties of polystyrene (PS) dishes incubated for 14 h with gram‐negative cells (Shewanella putrefaciens) were investigated by atomic force microscopy (AFM) in aqueous solutions at two pH values (4 and 10). The AFM images and force curves revealed the presence of a polymeric layer adsorbed onto the PS surfaces in acid media. In contrast, no evolution was observed in the case of basic media. Copyright © 2007 John Wiley & Sons, Ltd.     

Multiscale dynamics of the cell envelope of Shewanella putrefaciens as a response to pH change

The bacterial surface properties of gram-negative Shewanella putrefaciens were characterized by microbial adhesion to hydrocarbons (MATH), adhesion to polystyrene dishes, and electrophoresis at different values of pH and ionic strength. The bacterial adhesion to these two apolar substrates shows significant variations according to pH and ionic strength. Such behavior could be partly explained by electrostatic repulsions between bacteria and the solid or liquid interface. However, a similar trend was also observed at rather high ionic strength where electrostatic interactions are supposed to be screened. The nanomechanical properties at pH 4 and 10 and at high ionic strength were investigated by using atomic force microscopy (AFM). The indentation curves revealed the presence of a polymeric external layer that swells and softens up with increasing pH. This suggests a concomitant increase of the water permeability and so did of the hydrophilicity of the bacterial surface. Such evolution of the bacterial envelope in response to changes in pH brings new insight to the pH dependence in the bacterial adhesion tests. It especially demonstrates the necessity to consider the hydrophobic/hydrophilic surface properties of bacteria as not univocal for the various experimental conditions investigated.     

Effect Of Propene, <Emphasis Type="Italic">n</Emphasis>-Decane,and Toluene Plasma Kinetics on NO Conversion in Homogeneous Oxygen-Rich Dry Mixtures at Ambient Temperature

A photo-triggered discharge is used to study the influence of three hydrocarbons (HCs), propene (C₃H₆), n-decane (C₁₀H₂₂), and toluene (C₆H₅CH₃) on NO conversion in N₂/O₂/NO/HC mixtures, with 18.5% O₂ concentration, 700 ppm of NO, and an hydrocarbon concentration ranging between 190 ppm and 2,700 ppm. The electrical system generates a transient homogeneous plasma, working under 400 mbar total pressure, with a 50 ns short current pulse at a repetition frequency up to a few Hz. The NO concentration at the exit of the reactor is quantified using absolute FTIR spectroscopy measurements, as a function of the specific deposited energy in the discharge and the mixture composition. Owing to the plasma homogeneity, the experimental results can be compared to predictions of a self-consistent 0-D discharge and kinetic model based on available data in the literature about reactions and their rate constants. It is shown that the addition of either propene (as for DBD or corona discharges) or n-decane to N₂/O₂/NO leads to an improvement of the NO removal as compared to the mixture without hydrocarbon molecules. The adopted kinetic schemes explain this effect for the two mixture types. On the other hand, both the experiments and model predictions emphasize that the addition of toluene does not lead to the improvement of NO conversion. Moreover, compounds that are useful for NO _x reduction catalysis, such as aldehydes, are less produced in the mixture with toluene.     

Radicaux libres dérivés de sucres. V. Dérivés d'osamines N-hydroxylées et composés voisins Communication préliminaire

Free sugar radicals. V. Deoxyhydroxylaminosugar derivatives and related compounds We describe several synthetic routes to deoxyhydroxylaminosugar derivatives of the type Glyc-N(OH)-R where Glyc stands for a sugar moiety linked by any of its C-atoms except the anomeric one and R for one of the following substituants: H-atom, acyl, phosphoryl groups, aminoacid or sugar residues. Compounds of the above structure are potentially close analogs, homoisosteres, ? NOH? replacing ? O? , of biochemically important molecules. Under aerobic conditions, solutions of these derivatives contain minute concentrations of the corresponding nitroxide radicals which do not decrease significantly the resolution of the NMR. spectra but render these compounds usable as a new kind of spin labels. Spectroscopic properties (¹H-NMR., ¹³C-NMR., ESR.) of some of these compounds are reported.