Involvement of free radicals in peroxidatic reactions catalyzed by chloroperoxidase

The mechanism of chloroperoxidase (CPO)-catalyzed peroxidatic reactions of several substituted hydroquinones was studied at various hydrogen peroxide concentrations. The pathway was studied using cytochrome c as the radical trapping agent. As the hydroquinones became more hindered there was a difference in the amount of radicals trapped. For hydroquinone, 59.3% radical pathway, and methylhydroquinone, 81.4% radical, the difference in radicals trapped is due to a difference in pathway. For 2,3-dimethylhydroquinone (75.4%), trimethylhydroquinone (44.5%), and t-butylhydroquinone (0%) other non-peroxidatic reactions are noticed. Thus, for the more substituted hydroquinones the difference in radicals trapped can not be assigned to a difference in radical pathway. Also, there were problems drawing conclusions for this system due to the catalytic reaction of hydrogen peroxide. The radical trapping ability of 2,4,6-trimethylphenol was investigated for various other substrates. TMP reacted with the radicals generated in the enzymatic reactions of phenol, resorcinol, and m-methoxyphenol. Thus, this TMP system offers further potential as another radical trapping agent for use in these studies.

The influence of inert impurities on the catalyst lifetime and properties of nanofibrous carbon produced by utilization of diluted hydrocarbon gases

Experimental studies were focused on the feasibility of utilization of hydrocarbons diluted with inert gases (such as associated oil gases) during the synthesis of nanofibrous carbon. The carbon yield and catalyst lifetime were studied regarding the initial reaction mixture parameters. Varying the composition of the initial gas mixture, it is possible to control textural characteristics of the resulting carbon product.

Stories of reform in science education : commentary on opp(reg)ressive policies and tempered radicals

This response to the two papers (by Rodriguez and Carlone et al.) on science education reform acknowledges first the coherence of the arguments presented around four reform narratives; that of the process of becoming science-enthusiastic, the nature of beliefs of science reform teachers, the barriers to reform, and the institutional expressions of these barriers. In the commentary I first discuss the reform ‘problem’ in terms of two interacting issues—the purposes of school science and the value placed on it in an elementary school curriculum. The insights produced in these papers are then used to reflect on a range of experiences and current policy debates in Australia. Finally, in this commentary, I point out: (a) the relationship of the papers to the reform issue of opposition to Standards Based Science (SBS) from proponents’ traditional conceptions of science education, discussing how this more specific reform question relates to the two papers; and (b) the singular nature of the I-meanings characterised in the Carlone et al. paper, describing (using Australian examples) how the notions of tempered radicals and I-meanings might also be used to characterise complexities in the processes of school science reform.

Evolution of cuticular hydrocarbon diversity in ants

The cuticular hydrocarbons (CHCs) of ants provide important cues for nestmate and caste recognition. There is enormous diversity in the composition of these CHCs, but the manner in which this diversity has evolved is poorly understood. We gathered data on CHC profiles for 56 ant species, relating this information to their phylogeny. We deduced the mode of evolution of CHC profiles by reconstructing character evolution and then relating the number of changes in CHC components along each branch of the phylogeny to the length of the branch. There was a strong correlation between branch length and number of component changes, with fewer changes occurring on short branches. Our analysis thereby indicated a gradual mode of evolution. Different ant species tend to use specific CHC structural types that are exclusive of other structural types, indicating that species differences may be generated in part by switching particular biosynthetic pathways on or off in different lineages. We found limited, and contradictory, evidence for abiotic factors (temperature and rainfall) driving change in CHC profiles.

Measurement of forces due to structure in hydrocarbon liquids

Direct measurements of the force between two molecularly smooth mica sheets immersed in cyclohexane show not a monotonic van der Waals attraction, but an oscillatory function of distance, where the spacing between successive minima corresponds to the molecular diameter of cyclohexane. As surface separation increases the oscillations become less pronounced, and beyond 5 nm (typically seven or eight oscillations) they are no longer detected. These results accord with theoretical ideas on structural forces resulting from the inhomogeneous arrangement of molecules of the liquid near the solid surface. In n-octane the force law does not show the same pronounced oscillations, except at very small separations where repulsive barriers are found. These are attributed to the difficulty of removing the last layers of adsorbed molecules of the liquid from the mica surfaces, and they reduce the mice-mica adhesion significantly. Small amounts of water in the hydrocarbon liquids condense to form a bridge between the surfaces at small separations, causing a very strong adhesion between them. Some implications of these results for the stability of colloids in organic media are discussed.

In support of hydrocarbon exploration and discovery using clouds

Seismic data gathered from the Hydrocarbon Exploration and Discovery Operation is essential to identify possible hydrocarbon existence in a geologically surveyed area. However, the discovery operation takes a long time to be completed and computational processing of the acquired data is often delayed. Hydrocarbon exploration may end up needlessly covering an area without any hydrocarbon traces due to lack of immediate feedback from geophysical experts. This feedback can only be given when the acquired seismic data is computationally processed, analysed and interpreted. In response, we propose a comprehensive model to facilitate Hydrocarbon Exploration and Discovery Operation using encryption, decryption, satellite transmission and clouds. The model details the logical design of Seismic Data Processing (SDP) that exploits clouds and the ability for geophysical experts to provide on-line decisions on how to progress the hydrocarbon exploration operation at a remote location. Initial feasibility assessment was carried out to support our model. The SDP, data encryption and encryption for the assessment were carried out on a private cloud. The assessment shows that the overall process of hydrocarbon exploration from data acquisition, satellite data transmission through to SDP could be executed in a short time and at low costs.

Quality of service-based service level agreement management framework for hydrocarbon exploration and discovery operation

 The major contributions presented in this thesis are twofold. Firstly, it presents the research towards a unique services-based Hydrocarbon Exploration and Discovery Model that demonstrates the feasibility of using advanced ICT technologies in the reproduction of stages involved in an oil and gas discovery, processing and analysis process. Secondly, the research demonstrated a solution of the problems in providing agreed level of quality of service (QoS) and formalizing of appropriate Service Level Agreements (SLA) within such complex environment where different services within the model can be delivered by a variety of service providers

Rhamnolipid produced from agroindustrial wastes enhances hydrocarbon biodegradation in contaminated soil

A crude biosurfactant solution was produced by Pseudomonas aeruginosa growing on agroindustrial wastes as the substrate and used to study its effect on hydrocarbon biodegradation by the indigenous soil microflora under laboratory conditions. Two concentrations were studied at first and 1 mg of biosurfactant/g of soil showed to be the most efficient for the total petroleum hydrocarbon reduction, which reached 85% at the first 20 days in soil microcosms. Respirometric and microbial analyses showed that the biosurfactant added did not have toxic effects over the microbial population. The use of a biosurfactant for bioremediation has been limited because of its high cost production. Biosurfactants produced from cost-free by-products combines waste minimization with economic potential bioremediation process.

The reactivity of oytho-methoxy-substituted catechol radicals with sulfhydryl groups: Contribution for the comprehension of the mechanism of inhibition of NADPH oxidase by apocynin

Redox processes are involved in the mechanism of action of NADPH oxidase inhibitors such as diphenyleneiodonium and apocynin. Here, we studied the structure-activity relationship for apocynin and analogous ortho-methoxy-substituted catechols as inhibitors of the NADPH oxidase in neutrophils and their reactivity with peroxidase. Aiming to alter the reduction potential, the ortho-methoxy-catechol moiety was kept constant and the substituents at para position related to the hydroxyl group were varied. Two series of compounds were employed: methoxy-catechols bearing electron-withdrawing groups (MC-W) such as apocynin, vanillin, 4-nitroguaiacol, 4-cyanoguaiacol, and methoxy-catechol bearing electron-donating groups (MC-D) such as 4-methylguaiacol and 4-ethylguaiacol. We found that MC-D were weaker inhibitors compared to MD-W. Furthermore, the radicals generated by oxidation of MC-W via MPO/H(2)O(2), but not for MC-D, were able to oxidize glutathione (GSH) as verified by the formation of thiyl radicals, depletion of GSH, and recycling of the ortho-methoxy-catechols during their oxidations. The capacity of oxidizing sulfhydryl (SH) groups was also verified when ovalbumin was incubated with MC-W, but not for MC-D. Since the effect of apocynin has been correlated with inactivation of the cytosolic fractions of the NADPH oxidase complex and its oxidation during the inhibitory process develops a special role in this process, we suggest that the close relationship between the reactivity of the radicals of MC-W compounds with thiol groups and their efficacy as NADPH oxidase inhibitor could be the chemical pathway behind the mechanism of action of apocynin and should be taken into account in the design of new and specific NADPH oxidase inhibitors. (c) 2007 Elsevier B.V. All rights reserved.