Emission of Methane by Eudrilus eugeniae and Other Earthworms from Brazil

Earthworms emit denitrification-derived nitrous oxide and fermentation-derived molecular hydrogen. The present study demonstrated that the earthworm Eudrilus eugeniae, obtained in Brazil, emitted methane. Other worms displayed a lesser or no capacity to emit methane. Gene and transcript analyses of mcrA (encoding the alpha subunit of methyl-CoM reductase) in gut contents of E. eugeniae suggested that Methanosarcinaceae, Methanobacteriaceae, and Methanomicrobiaceae might be associated with this emission.

Release of NO from a nitrosyl ruthenium complex through oxidation of mitochondrial NADH and effects on mitochondria

Nitrosyl ruthenium complexes are promising NO donor agents with numerous advantages for the biologic applications of NO. We have characterized the NO release from the nitrosyl ruthenium complex [Ru(NO2)(bpy)(2)(4-pic)](+) (I) and the reactive oxygen/nitrogen species (ROS/RNS)-mediated NO actions on isolated rat liver mitochondria. The results indicated that oxidation of mitochondrial NADH promotes NO release from (I) in a manner mediated by NO2 formation (at neutral pH) as in mammalian cells, followed by an oxygen atom transfer mechanism (OAT). The NO released from (I) uncoupled mitochondria at low concentrations/incubation times and inhibited the respiratory chain at high concentrations/incubation times. In the presence of ROS generated by mitochondria NO gave rise to peroxynitrite, which, in turn, inhibited the respiratory chain and oxidized membrane protein-thiols to elicit a Ca2+-independent mitochondrial permeability transition; this process was only partially inhibited by cyclosporine-A, almost fully inhibited by the thiol reagent N-ethylmaleimide (NEM) and fully inhibited by the NO scavenger 2-(4-carboxyphenyl)-4,45,5-tetramethylimidazoline-1-oxyl-3-oxide (cPTIO). These actions correlated with the release of cytochrome c from isolated mitochondria as detected by Western blotting analysis. These events, typically involved in cell necrosis and/or apoptosis denote a potential specific action of (I) and analogs against tumor cells via mitochondria-mediated processes. (C) 2012 Elsevier Inc. All rights reserved.

Functionalization of gold and silver nanoparticles with diphenyl dichalcogenides probed by surface enhanced Raman scattering

This paper describes a surface-enhanced Raman scattering (SERS) systematic investigation regarding the functionalization of gold (Au) and silver (Ag) nanoparticles with diphenyl dichalcogenides, i.e. diphenyl disulfide, diphenyl diselenide, and diphenyl ditelluride. Our results showed that, in all cases, functionalization took place with the cleavage of the chalcogenchalcogen bond on the surface of the metal. According to our density functional theory calculations, the molecules assumed a tilted orientation with respect to the metal surface for both Au and Ag, in which the angle of the phenyl ring relative to the metallic surface decreased as the mass of the chalcogen atom increased. The detected differences in the ordinary Raman and SERS spectra were assigned to the distinct stretching frequencies of the carbonchalcogen bond and its relative contribution to the ring vibrational modes. In addition, the SERS spectra showed that there was no significant interaction between the phenyl ring and the surface, in agreement with the tilted orientation observed from our density functional theory calculations. The results described herein indicate that diphenyl dichalcogenides can be successfully employed as starting materials for the functionalization of Au nanoparticles with organosulfur, organoselenium, and organotellurium compounds. On the other hand, diphenyl disulfide and diphenyl diselenide could be employed for the functionalization of Ag nanoparticles, while the partial oxidation of the organotellurium unit could be detected on the Ag surface. Copyright (C) 2011 John Wiley & Sons, Ltd.

Oxidation of lysergic acid diethylamide (LSD) by peroxidases: a new metabolic pathway

Lysergic acid diethylamide (LSD) is a potent hallucinogen that is primarily metabolized to 2-oxo-3-hydroxy-LSD (O-H-LSD) and N-desmethyl-LSD (nor-LSD) by cytochrome P450 complex liver enzymes. Due to its extensive metabolism, there still is an interest in the identification of new metabolites and new routes of its metabolism in humans. In the present study, we investigated whether LSD could be a substrate for horseradish peroxidase or myeloperoxidase (MPO). Using liquid chromatography coupled to UV detection and electrospray ionization mass spectrometry (LC-UV-ESI-MS), we found that both peroxidases were capable of metabolizing LSD to the same compounds that have been observed in vivo (i.e., O-H-LSD and nor-LSD). In addition, we found another major metabolite, N,N-diethyl-7-formamido-4-methyl-6-oxo-2,3,4,4a,5,6-hexahydrobenzo[f]quinoline-2-carboxamide (FOMBK), which is an opened indolic ring compound. Hydrolysis of FOMBK led to the deformylated compound 7-amino-N,N-diethyl-4-methyl-6-oxo-2,3,4,4a,5,6-hexahydrobenzo[f]quinoline-2-carboxamide. The reactions of LSD with the peroxidases were chemiluminescent and sensitive to inhibition by reactive oxygen scavengers, which indicated that the classic peroxidase cycle is involved in this new alternative metabolic pathway. Considering that MPO is abundant in immune cells and also present in the central nervous system, the degradation pathway described in this study suggests a possible route of LSD metabolism that may occur concurrently with the in vivo reaction catalyzed by the cytochrome P450 system.

Synthesis of Chromanes and 4H-Chromenes: Exploring the Oxidation of 2H-Chromenes and Dihydro-1-benzoxepines by Hypervalent Iodine(III)

The reaction of various oxygen-containing benzo-fused cycloalkenes were studied with the hypervalent iodine reagent hydroxy(tosyloxy) iodo]benzene [PhI(OH)OTs, HTIB]. 2H-Chromene and 4-methyl-2H-chromene resulted in substituted 4H-chromene and cis-3,4-dialkoxy-4-methyl-3,4-dihydro-2H-chromenes, respectively. Ring contraction to chromanes and benzofurans was observed for dihydrobenzoxepines and 2,2-dimethyl-2H-chromenes, respectively.

Biomimetic in vitro oxidation of lapachol: A model to predict and analyse the in vivo phase I metabolism of bioactive compounds

The bioactive naphtoquinone lapachol was studied in vitro by a biomimetic model with Jacobsen catalyst (manganese(III) salen) and iodosylbenzene as oxidizing agent. Eleven oxidation derivatives were thus identified and two competitive oxidation pathways postulated. Similar to Mn(III) porphyrins, Jacobsen catalyst mainly induced the formation of para-naphtoquinone derivatives of lapachol, but also of two ortho-derivatives. The oxidation products were used to develop a GC MS (SIM mode) method for the identification of potential phase I metabolites in vivo. Plasma analysis of Wistar rats orally administered with lapachol revealed two metabolites, alpha-lapachone and dehydro-alpha-lapachone. Hence, the biomimetic model with a manganese salen complex has evidenced its use as a valuable tool to predict and elucidate the in vivo phase I metabolism of lapachol and possibly also of other bioactive natural compounds. (C) 2012 Elsevier Masson SAS. All rights reserved.

Comparative performance evaluation of hepatitis C virus genotyping based on the 5' untranslated region versus partial sequencing of the NS5B region of brazilian patients with chronic hepatitis C

Background Genotyping of hepatitis C virus (HCV) has become an essential tool for prognosis and prediction of treatment duration. The aim of this study was to compare two HCV genotyping methods: reverse hybridization line probe assay (LiPA v.1) and partial sequencing of the NS5B region. Methods Plasma of 171 patients with chronic hepatitis C were screened using both a commercial method (LiPA HCV Versant, Siemens, Tarrytown, NY, USA) and different primers targeting the NS5B region for PCR amplification and sequencing analysis. Results Comparison of the HCV genotyping methods showed no difference in the classification at the genotype level. However, a total of 82/171 samples (47.9%) including misclassification, non-subtypable, discrepant and inconclusive results were not classified by LiPA at the subtype level but could be discriminated by NS5B sequencing. Of these samples, 34 samples of genotype 1a and 6 samples of genotype 1b were classified at the subtype level using sequencing of NS5B. Conclusions Sequence analysis of NS5B for genotyping HCV provides precise genotype and subtype identification and an accurate epidemiological representation of circulating viral strains.

Estimating reaction constants by ab initio molecular modeling: a study on the oxidation of phenol to catechol and hydroquinone in advanced oxidation processes

Molecular modeling is growing as a research tool in Chemical Engineering studies, as can be seen by a simple research on the latest publications in the field. Molecular investigations retrieve information on properties often accessible only by expensive and time-consuming experimental techniques, such as those involved in the study of radical-based chain reactions. In this work, different quantum chemical techniques were used to study phenol oxidation by hydroxyl radicals in Advanced Oxidation Processes used for wastewater treatment. The results obtained by applying a DFT-based model showed good agreement with experimental values available, as well as qualitative insights into the mechanism of the overall reaction chain. Solvation models were also tried, but were found to be limited for this reaction system within the considered theoretical level without further parameterization.

Oxidation of Copper(I) in seawater at nanomolar levels

The oxidation and reduction of copper in air-saturated seawater and NaCl solutions has been measured as a function of pH (7.17-8.49), temperature (5-35ºC) and ionic strength (0.1-0.7 M). The oxidation rate was fitted to an equation for sodium chloride and seawater valid at different pH and media conditions: k . . pH- . /T- . I . I k . . pH- . /T- . I . I (sw) (NaCl) log 5 036 0 514 1764 915 1101 0 233 log 5 221 0 609 1915 433 1818 0 408 = + + = + + The reduction of Cu(II) was studied in both media for different initial concentration of copper(II). When the initial Cu(II) concentration was 200 nM, the copper(I) produced was 20% and 9% for NaCl and seawater, respectively. Considering the copper(I) reduced from Cu(II), the speciation and the contribution of these species to the kinetic process was studied. The Cu(I) speciation is dominated by the CuCl2 - species. On the other hand, the neutral chloride CuCl species dominates the Cu(I) oxidation in the range 0.1 M to 0.7 M chloride concentrations.

Partial reconstruction of the trajectories of a discretely observed branching diffusion with immigration and an application to inference

In this treatise we consider finite systems of branching particles where the particles move independently of each other according to d-dimensional diffusions. Particles are killed at a position dependent rate, leaving at their death position a random number of descendants according to a position dependent reproduction law. In addition particles immigrate at constant rate (one immigrant per immigration time). A process with above properties is called a branching diffusion withimmigration (BDI). In the first part we present the model in detail and discuss the properties of the BDI under our basic assumptions. In the second part we consider the problem of reconstruction of the trajectory of a BDI from discrete observations. We observe positions of the particles at discrete times; in particular we assume that we have no information about the pedigree of the particles. A natural question arises if we want to apply statistical procedures on the discrete observations: How can we find couples of particle positions which belong to the same particle? We give an easy to implement 'reconstruction scheme' which allows us to redraw or 'reconstruct' parts of the trajectory of the BDI with high accuracy. Moreover asymptotically the whole path can be reconstructed. Further we present simulations which show that our partial reconstruction rule is tractable in practice. In the third part we study how the partial reconstruction rule fits into statistical applications. As an extensive example we present a nonparametric estimator for the diffusion coefficient of a BDI where the particles move according to one-dimensional diffusions. This estimator is based on the Nadaraya-Watson estimator for the diffusion coefficient of one-dimensional diffusions and it uses the partial reconstruction rule developed in the second part above. We are able to prove a rate of convergence of this estimator and finally we present simulations which show that the estimator works well even if we leave our set of assumptions.

Selective photo-oxidation of cellobiose with tio2-supported metal nanoparticles

Upgrade of biomass to valuable chemicals is a central topic in modern research due to the high availability and low price of this feedstock. For the difficulties in biomass treatment, different pathways are still under investigation. A promising way is in the photodegradation, because it can lead to greener transformation processes with the use of solar light as a renewable resource. The aim of my work was the research of a photocatalyst for the hydrolysis of cellobiose under visible irradiation. Cellobiose was selected because it is a model molecule for biomass depolymerisation studies. Different titania crystalline structures were studied to find the most active phase. Furthermore, to enhance the absorption of this semiconductor in the visible range, noble metal nanoparticles were immobilized on titania. Gold and silver were chosen because they present a Surface Plasmon Resonance band and they are active metals in several photocatalytic reactions. The immobilized catalysts were synthesized following different methods to optimize the synthetic steps and to achieve better performances. For the same purpose the alloying effect between gold and silver nanoparticles was examined.

Using sulfur isotope fractionation to understand the atmospheric oxidation of SO 2

Sulfate aerosol plays an important but uncertain role in cloud formation and radiative forcing of the climate, and is also important for acid deposition and human health. The oxidation of SO2 to sulfate is a key reaction in determining the impact of sulfate in the environment through its effect on aerosol size distribution and composition. This thesis presents a laboratory investigation of sulfur isotope fractionation during SO2 oxidation by the most important gas-phase and heterogeneous pathways occurring in the atmosphere. The fractionation factors are then used to examine the role of sulfate formation in cloud processing of aerosol particles during the HCCT campaign in Thuringia, central Germany. The fractionation factor for the oxidation of SO2 by ·OH radicals was measured by reacting SO2 gas, with a known initial isotopic composition, with ·OH radicals generated from the photolysis of water at -25, 0, 19 and 40°C (Chapter 2). The product sulfate and the residual SO2 were collected as BaSO4 and the sulfur isotopic compositions measured with the Cameca NanoSIMS 50. The measured fractionation factor for 34S/32S during gas phase oxidation is αOH = (1.0089 ± 0.0007) − ((4 ± 5) × 10−5 )T (°C). Fractionation during oxidation by major aqueous pathways was measured by bubbling the SO2 gas through a solution of H2 O2

Sources and pathways of methane formed in oxidative environments

Methane is the most abundant reduced organic compound in the atmosphere. As the strongest known long-lived greenhouse gas after water vapour and carbon dioxide methane perturbs the radiation balance of Earth’s atmosphere. The abiotic formation of methane requires ultraviolet irradiation of organic matter or takes place in locations with high temperature and/or pressure, e.g. during biomass burning or serpentinisation of olivine, under hydrothermal conditions in the oceans deep or below tectonic plates. The biotic methane formation was traditionally thought to be formed only by methanogens under strictly anaerobic conditions, such as in wetland soils, rice paddies and agricultural waste. rnIn this dissertation several chemical pathways are described which lead to the formation of methane under aerobic and ambient conditions. Organic precursor compounds such as ascorbic acid and methionine were shown to release methane in a chemical system including ferrihydrite and hydrogen peroxide in aquatic solution. Moreover, it was shown by using stable carbon isotope labelling experiments that the thio-methyl group of methionine was the carbon precursor for the methane produced. Methionine, a compound that plays an important role in transmethylation processes in plants was also applied to living plants. Stable carbon isotope labelling experiments clearly verified that methionine acts as a precursor compound for the methane from plants. Further experiments in which the electron transport chain was inhibited suggest that the methane generation is located in the mitochondria of the plants. The abiotic formation of methane was shown for several soil samples. Important environmental parameter such as temperature, UV irradiation and moisture were identified to control methane formation. The organic content of the sample as well as water and hydrogen peroxide might also play a major role in the formation of methane from soils. Based on these results a novel scheme was developed that includes both biotic and chemical sources of methane in the pedosphere.rn

Selective oxidation of 5-hydroxymethylfurfural using monometallic and bimetallic supported nanoparticles

This work deals with the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) using metal supported catalysts. Catalysts were prepared from the immobilisation of preformed monometallic (Au, Pd) and bimetallic (AuCu, AuPd) nanoparticles on commercial oxides (TiO2, CeO2). Au-TiO2 catalyst was found to be very active for HMF oxidation; however, this system deactivated very fast. For this reason, we prepared bimetallic gold-copper nanoparticles and an increase in the catalytic activity was observed together with an increase in catalyst stability. In order to optimise the interaction of the metal active phase with the support, Au and AuCu nanoparticles were supported onto CeO2. Au-CeO2 catalyst was found to be more active than the bimetallic one, leading to the conclusion that in this case the most important feature is the interaction between gold and the support. Catalyst pre-treatments (calcination and washing) were carried out to maximise the contact between the metal and the oxide and an increase in the FDCA production could be observed. The presence of ceria defective sites was crucial for FDCA formation. Mesoporous cerium oxide was synthesised with the hard template method and was used as support for Au nanoparticles to promote the catalytic activity. In order to study the role of active phase in HMF oxidation, PdAu nanoparticles were supported onto TiO2. Au and Pd monometallic catalysts were very active in the formation of HMFCA (5-hydroxymethyl-2-furan carboxylic acid), but Pd was not able to convert it, leading to a low FDCA yield. The calcination of PdAu catalysts led to Pd segregation on the particles surface, which changed the reaction pathway and included an important contribution of the Cannizzaro reaction. PVP protected PdAu nanoparticles, synthesised with different morphologies (core-shell and alloyed structure), confirmed the presence of a different reaction mechanism when the metal surface composition changes.