Determination of activation energy distributions for chemisorption of oxygen on carbon: an improved approach

The present paper proposes an approach to obtaining the activation energy distribution for chemisorption of oxygen onto carbon surfaces, while simultaneously allowing for the activation energy dependence of the pre-exponential factor of the rate constant. Prior studies in this area have considered this factor to be uniform, thereby biasing estimated distributions. The results show that the derived activation energy distribution is not sensitive to the chemisorption mechanism because of the step function like property of the coverage. The activation energy distribution is essentially uniform for some carbons, and has two or possibly more discrete stages, suggestive of at least two types of sites, each with its own uniform distribution. The pre-exponential factors of the reactions are determined directly from the experimental data, and are found not to be constant as assumed in earlier work, but correlated with the activation energy. The latter results empirically follow an exponential function, supporting some earlier statistical and experimental work. The activation energy distribution obtained in the present paper permits improved correlation of chemisorption data in comparison to earlier studies. (C) 2000 Elsevier Science Ltd. All rights reserved.

Expression, purification, and characterization of biol: A carbon-carbon bond cleaving cytochrome P450 involved in biotin biosynthesis in Bacillus subtilis

Pimelic acid formation for biotin biosynthesis in Bacillus subtilis has been proposed to involve a cytochrome P450 encoded by the gene biol. We have subcloned bioI and overexpressed the encoded protein, BioI. A purification protocol was developed utilizing ion exchange, gel filtration, and hydroxyapatite chromatography, Investigation of the purified BioI by UV-visible spectroscopy revealed spectral properties characteristic of a cytochrome P450 enzyme. BioI copurifies with acylated Escherichia coil acyl carrier protein (ACP), suggesting that in vivo a fatty acid substrate may be presented to BioI as an acyl-ACP. A combination of electrospray mass spectrometry of the intact acyl-ACP and GCMS indicated a range of fatty acids were bound to the ACP. A catalytically active system has been established employing E. coli flavodoxin reductase and a novel, heterologous flavodoxin as the redox partners for BioI. In this system, BioI cleaves a carbon-carbon bond of an acyl-ACP to generate a pimeloyl-ACP equivalent, from which pimelic acid is isolated after base-catalyzed saponification. A range of free fatty acids have also been explored as potential alternative substrates for BioI, with C16 binding most tightly to the enzyme. These fatty acids are also metabolized to dicarboxylic acids, but with less regiospecificity than is observed with acyl-ACPs. A possible mechanism for this transformation is discussed. These results strongly support the proposed role for BioI in biotin biosynthesis. In addition, the production of pimeloyl-ACP explains the ability of BioI to function as a pimeloyl CoA source in E. coli, which, unlike B. subtilis, is unable to utilize free pimelic acid for biotin production. (C) 2000 Academic Press.

Unifying principles in terrestrial locomotion: Do hopping Australian marsupials fit in?

Mammalian terrestrial locomotion has many unifying principles. However, the Macropodoidea are a particularly interesting group that exhibit a number of significant deviations from the principles that seem to apply to other mammals. While the properties of materials that comprise the musculoskeletal system of mammals are similar, evidence suggests that tendon properties in macropodoid marsupials may be size or function dependent, in contrast to the situation in placental mammals. Postural differences related to hopping versus running have a dramatic effect on the scaling of the pelvic limb musculoskeletal system. Ratios of muscle fibre to tendon cross-sectional areas for ankle extensors and digital flexors scale with positive allometry in all mammals, but exponents are significantly higher in macropods. Tendon safety factors decline with increasing body mass in mammals, with eutherians at risk of ankle extensor tendon rupture at a body mass of about 150 kg, whereas kangaroos encounter similar problems at a body mass of approximately 35 kg. Tendon strength appears to limit locomotor performance in these animals. Elastic strain energy storage in tendons is mass dependent in all mammals, but exponents are significantly larger in macropodid. Tibial stresses may scale with positive allometry in kangaroos, which result in lower bone safety factors in macropods compared to eutherian mammals.

Opposite roles of O-2 in NO- and N2O-carbon reactions: An ab initio study

Previous experimental studies showed that the presence of O-2 greatly enhances NO-carbon reaction while it depresses N2O-carbon reaction on carbon surfaces. A popular explanation for the rate increase is that the addition of O-2 results in a large number of reactive carbon-oxygen complexes, and decomposition of these complexes produces many more active sites. The explanation for the latter is that excess O-2 simply blocks the active sites, thus reducing the rate of N2O-carbon reaction. The contradiction is that O-2 can also occupy active sites in NO-carbon reaction and produce active sites in N2O-carbon reduction. By using ab initio calculation, we find that the opposite roles of O-2 are caused by the different manners of N2O and NO adsorption on the carbon surface. In the presence of excess O-2, most Of the active sites are occupied by oxygen groups. In the competition for the remaining active sites, NO is more likely to chemisorb in the form of NO2 and NO chemisorption is mon thermodynamically favorable than O-2 chemisorption. By contrast, the presence of excess O-2 makes N2O chemisorption much less thermally stable either on the consecutive edge sites or edge sites isolated by semiquinone oxygen. A detailed analysis and discussion of the reaction mechanism of N-2 formation from NO- and N2O-carbon reaction in the presence of O-2 is presented in this paper.

Prediction of carbon monoxide in fires by conditional moment closure

Carbon monoxide is the chief killer in fires. Dangerous levels of CO can occur when reacting combustion gases are quenched by heat transfer, or by mixing of the fire plume in a cooled under- or overventilated upper layer. In this paper, carbon monoxide predictions for enclosure fires are modeled by the conditional moment closure (CMC) method and are compared with laboratory data. The modeled fire situation is a buoyant, turbulent, diffusion flame burning under a hood. The fire plume entrains fresh air, and the postflame gases are cooled considerably under the hood by conduction and radiation, emulating conditions which occur in enclosure fires and lead to the freezing of CO burnout. Predictions of CO in the cooled layer are presented in the context of a complete computational fluid dynamics solution of velocity, temperature, and major species concentrations. A range of underhood equivalence ratios, from rich to lean, are investigated. The CMC method predicts CO in very good agreement with data. In particular, CMC is able to correctly predict CO concentrations in lean cooled gases, showing its capability in conditions where reaction rates change considerably.

Ecosystem process models at multiple scales for mapping tropical forest productivity

Quantifying mass and energy exchanges within tropical forests is essential for understanding their role in the global carbon budget and how they will respond to perturbations in climate. This study reviews ecosystem process models designed to predict the growth and productivity of temperate and tropical forest ecosystems. Temperate forest models were included because of the minimal number of tropical forest models. The review provides a multiscale assessment enabling potential users to select a model suited to the scale and type of information they require in tropical forests. Process models are reviewed in relation to their input and output parameters, minimum spatial and temporal units of operation, maximum spatial extent and time period of application for each organization level of modelling. Organizational levels included leaf-tree, plot-stand, regional and ecosystem levels, with model complexity decreasing as the time-step and spatial extent of model operation increases. All ecosystem models are simplified versions of reality and are typically aspatial. Remotely sensed data sets and derived products may be used to initialize, drive and validate ecosystem process models. At the simplest level, remotely sensed data are used to delimit location, extent and changes over time of vegetation communities. At a more advanced level, remotely sensed data products have been used to estimate key structural and biophysical properties associated with ecosystem processes in tropical and temperate forests. Combining ecological models and image data enables the development of carbon accounting systems that will contribute to understanding greenhouse gas budgets at biome and global scales.

Axial Young's modulus prediction of single-walled carbon nanotube arrays with diameters from nanometer to meter scales

Based on a self-similar array model, we systematically investigated the axial Young's modulus (Y-axis) of single-walled carbon nanotube (SWNT) arrays with diameters from nanometer to meter scales by an analytical approach. The results show that the Y-axis of SWNT arrays decreases dramatically with the increases of their hierarchy number (s) and is not sensitive to the specific size and constitution when s is the same, and the specific Young's modulus Y-axis(s) is independent of the packing configuration of SWNTs. Our calculations also show that the Y-axis of SWNT arrays with diameters of several micrometers is close to that of commercial high performance carbon fibers (CFs), but the Y-axis(s) of SWNT arrays is much better than that of high performance CFs. (C) 2005 American Institute of Physics.

Nitrogen- and carbon-based isomerism in the copper(II) complexes of 6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine

A number of N- and C-based diastereomeric copper(II) complexes of the pendant-arm macrocyclic hexaamines trans- and cis-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine (L-1 and L-2) have been isolated and characterised. The crystal structures of the complexes RRSS-[CuL1(OH2)(2)][ClO4](2), SSRR-[Cu(H2L1)(OClO3)(2)]-[ClO4](2) . 2H(2)O RSRS-[CuL1(OClO3)]ClO4, RSRS-[CuL2(OClO3)]ClO4 and RRSS-[Cu(H2L2)(OClO3)(2)][ClO4](2) have been determined. Some unusual structural and spectroscopic variations are found across this series of diastereomers. The protonation constants of the pendant primary amines are dependent on the relative dispositions of the adjacent macrocyclic secondary amine H atoms, which is indicative of intramolecular hydrogen-bonding interactions.

Macrocycle formation through carbon acid-formaldehyde condensation reactions of bis(propane-1,2-diamine)- and bis (2-methylpropane-1,2-diamine)-copper(II) ions

The reaction of the bis(1,2-diamine) copper(II) complexes of racemic propane-1,2-diamine (pn) and 2-methylpropane-1,2-diamine (dmen) with formaldehyde and nitroethane in methanol under basic conditions yields minor macrocyclic condensation products in addition to the major acyclic products. Where C-pendant methyl groups on the pair of coordinated diamines are in cis dispositions, the first -NH-CH2-C(CH3)(NO2)-CH2-NH- ring formation occurs at amine pairs distant from these C-methyl substituents, and further reaction to yield a macrocycle is not observed. However, where the C-methyl substituents are in trans dispositions, the chemistry proceeds to yield the macrocycle. Commencing with pn, trans-(6,13-diammonio-2,6,9,13-tetramethyl-1,4,7,10-tetraazacyclotetradecane)copper(II) perchlorate formed and crystallized in the space group P2(1)/n, with a 9.782(2), b 9.2794(6), c 17.017(4) Angstrom, beta 103.24(1)degrees. The copper ion is found in a square-planar environment, with the two methyl groups of the pn residues and the pairs of introduced pendant groups all in trans arrangements.

Effects of oxide promoters on metal dispersion and metal-support interactions in Ni catalysts supported on activated carbon

Various oxide-promoted Ni catalysts supported on activated carbon were prepared, and the effect of promoters on the surface structure and properties of Ni catalysts was studied. Physical adsorption (Na adsorption), thermogravimetric analysis (TGA), temperature-programmed desorption (TPD), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were used to characterize the catalysts. It is found that nickel is fairly uniformly distributed in the pores of the carbon support. Addition of promoters produces a more homogeneous distribution of nickel ion in carbon. However, distributions of promoters in the pores are varying. Addition of promoters increases the dispersion of nickel in carbon. Promoters also change the interaction between the carbon and Ni, resulting in significantly different behaviors of catalysts under various environments. CaO and MgO promoters improve the reactivity of nickel catalysts with O-2 but retard the interaction between nickel oxide and carbon. La2O3 shows some inhibiting effect on the interactions between nickel oxide and oxygen as well as carbon.

Hydrogen Storage by Carbon Nanotubes

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Carbon hydroxylation of alkyltetrahydropyranols: A paradigm for spiroacetal biosynthesis in Bactrocera sp.

[GRAPHICS] In a number of Bactrocera species the penultimate step in the biosynthesis of spiroacetals is shown to be the hydroxylation of an alkyltetrahydropyranol followed by cyclization, The monooxygenases that catalyze this side chain hydroxylation show a strong preference for oxidation four carbons from the hemiketal center, to produce the spiroacetal, The hydroxy spiroacetals observed in Bactrocera appear to derive from direct oxidation of the parent spiroacetals and not from alternate precursors.

A modified pore-filling isotherm for liquid-phase adsorption in activated carbon

This article modifies the usual form of the Dubinin-Radushkevich pore-filling model for application to liquid-phase adsorption data, where large molecules are often involved. In such cases it is necessary to include the repulsive part of the energy in the micropores, which is accomplished here by relating the pore potential to the fluid-solid interaction potential. The model also considers the nonideality of the bulk liquid phase through the UNIFAC activity coefficient model, as well as structural heterogeneity of the carbon. For the latter the generalized adsorption integral is used while incorporating the pore-size distribution obtained by density functional theory analysis of argon adsorption data. The model is applied here to the interpretation of aqueous phase adsorption isotherms of three different esters on three commercial activated carbons. Excellent agreement between the model and experimental data is observed, and the fitted Lennard-Jones size parameter for the adsorbate-adsorbate interactions compares well with that estimated from known critical properties, supporting the modified approach. On the other hand, the model without consideration of bulk nonideality, or when using classical models of the characteristic energy, gives much poorer bts of the data and unrealistic parameter values.