Degradation pathway of bisphenol A: Does ipso substitution apply to phenols containing a quaternary alpha-carbon structure in the para position?

The degradation of bisphenol A and nonylphenol involves the unusual rearrangement of stable carboncarbon bonds. Some nonylphenol isomers and bisphenol A possess a quaternary alpha-carbon atom as a common structural feature. The degradation of nonylphenol in Sphingomonas sp. strain TTNP3 occurs via a type II ipso substitution with the presence of a quaternary alpha-carbon as a prerequisite. We report here a new degradation pathway of bisphenol A. Consequent to the hydroxylation at position C-4, according to a type 11 ipso substitution mechanism, the C-C bond between the phenolic moiety and the isopropyl group of bisphenol A is broken. Besides the formation of hydroquinone and 4-(2-hydroxypropan-2-yl) phenol as the main metabolites, further compounds resulting from molecular rearrangements consistent with a carbocationic intermediate were identified. Assays with resting cells or cell extracts of Sphingomonas sp. strain TTNP3 under an 18 02 atmosphere were performed. One atom of 180, was present in hydroquinone, resulting from the monooxygenation of bisphenol A and nonylphenol. The monooxygenase activity was dependent on both NADPH and flavin adenine dinucleotide. Various cytochrome P450 inhibitors had identical inhibition effects on the conversion of both xenobiotics. Using a mutant of Sphingomonas sp. strain TTNP3, which is defective for growth on nonylphenol, we demonstrated that the reaction is catalyzed by the same enzymatic system. In conclusion, the degradation of bisphenol A and nonylphenol is initiated by the same monooxygenase, which may also lead to ipso substitution in other xenobiotics containing phenol with a quaternary a-carbon.

Pressure-dependent product distribution of citral hydrogenation over micelle-hosted Pd and Ru nanoparticles in supercritical carbon dioxide

In situ synthesis and testing of Ru and Pd nanoparticles as catalysts in the presence of ammonium perfluorohydrocarbo-carboxylate surfactant in supercritical carbon dioxide were carried out in a stainless steel batch reactor at 40 degrees C over a pressure range of 80-150 bar CO2/H-2. Direct Visualization of the formation of a supercritical phase at above 80 bar, followed by the formation of homogeneous microemulsions containing dispersed Ru nanoparticles and Pd nanoparticles in scCO(2) at above 95-100 bar, were conducted through a sapphire window reactor using a W-0 (molar water to surfactant ratio) of 30. The synthesised RU and Pd nanoparticles showed interesting product distributions in the selective hydrogenation of organic molecules, depending critically oil the density and polarity of the fluid (which ill turn depends on the pressure applied). Thus, selective hydrogenation of the citral molecule, which contains three reducible groups (aldehydes and double bonds at the 23 and 6,7 positions), is feasible Lis a chemical probe. (c) 2005 Elsevier Inc. All rights reserved.

Micelle-hosted palladium nanoparticles catalyze citral molecule hydrogenation in supercritical carbon dioxide

A new approach of employing metal particles in micelles for the hydrogenation of organic molecules in the presence of fluorinated surfactant and water in supercritical carbon dioxide has very recently been introduced. This is allegedly to deliver many advantages for carrying out catalysis including the use of supercritical carbon dioxide (scCO(2)) as a greener solvent. Following this preliminary account, the present work aims to provide direct visual evidence on the formation of metal microemulsions and to investigate whether metal located in the soft micellar assemblies could affect reaction selectivity. Synthesis of Pd nanoparticles in perfluorohydrocarboxylate anionic micelles in scCO(2) is therefore carried out in a stainless steel batch reactor at 40 degreesC and in a 150 bar CO2/H-2 mixture. Homogeneous dispersion of the microemulsion containing Pd nanoparticles in scCO(2) is observed through a sapphire window reactor at W-0 ratios (molar water-to-surfactant ratios) ranging from 2 to 30. It is also evidenced that the use of micelle assemblies as new metal catalyst nanocarriers could indeed exert a great influence on product selectivity. The hydrogenation of a citral molecule that contains three reducible groups (aldehyde, double bonds at the 2,3-position and the 6,7-position) is studied. An unusually high selectivity toward citronellal (a high regioselectivity toward the reduction of the 2,3-unsaturation) is observed in supercritical carbon dioxide. On the other hand, when the catalysis is carried out in the conventional liquid or vapor phase over the same reaction time, total hydrogenation of the two double bonds is achieved. It is thought that the high kinetic reluctance for double bond hydrogenation of the citral molecule at the hydrophobic end (the 6,7-position) is due to the unique micelle environment that is in close proximity to the metal surface in supercritical carbon dioxide that guides a head-on attack of the molecule toward the core metal particle.

Inelastic neutron scattering in spectroscopic studies of hydrogen on carbon-supported catalysts-experimental spectra and computed spectra of model systems

Inelastic neutron scattering spectroscopy has been used to observe and characterise hydrogen on the carbon component of a Pt/C catalyst. INS provides the complete vibration spectrum of coronene, regarded as a molecular model of a graphite layer. The vibrational modes are assigned with the aid of ab initio density functional theory calculations and the INS spectra by the a-CLIMAX program. A spectrum for which the H modes of coronene have been computationally suppressed, a carbon-only coronene spectrum, is a better representation of the spectrum of a graphite layer than is coronene itself. Dihydrogen dosing of a Pt/C catalyst caused amplification of the surface modes of carbon, an effect described as H riding on carbon. From the enhancement of the low energy carbon modes (100-600 cm(-1)) it is concluded that spillover hydrogen becomes attached to dangling bonds at the edges of graphitic regions of the carbon support. (C) 2003 Elsevier Science B.V. All rights reserved.

Heterogeneously catalyzed asymmetric hydrogenation of C = C bonds directed by surface-tethered chiral modifiers

Asymmetric hydrogenation of C=C bonds is of the highest importance in organic synthesis, and such reactions are currently carried out with organometallic homogeneous catalysts. Achieving heterogeneous metal-catalyzed hydrogenation, a highly desirable goal, necessitates forcing the crucial enantiodifferentiating step to take place at the metal surface. By synthesis and application of six chiral sulfide ligands that anchor robustly to Pd nanoparticles and resist displacement, we have for the first time accomplished heterogeneous enantioselective catalytic hydrogenation of isophorone. High resolution XPS data established that ligand adsorption from solution occurred exclusively on the Pd nanoparticles and not on the carbon support. All ligands contained a pyrrolidine nitrogen to enable their interaction with the isophorone substrate while the sulfide functionality provided the required interaction with the Pd surface. Enantioselective turnover numbers of up to similar to 100 product molecules per ligand molecule were found with a very large variation in asymmetric induction between ligands: observed enantiomeric excesses increased with increasing size of the alkyl group in the sulfide. This likely reflects varying degrees of ligand dispersion on the surface: bulky substituent groups hinder close approach of ligand molecules to each other, inhibiting close-packed island formation, favoring dispersion as separate molecules, and leading to effective asymmetric induction. Conversely, small substituents favor island formation leading to very low asymmetric induction. Enantioselective reaction most likely involves initial formation of an enamine or iminium species, confirmed by use of an analogous tertiary amine, which leads to racemic product. Ligand rigidity and resistance to self-assembled monolayer formation are important attributes that should be designed into improved chiral modifiers.

Rational modification of the hierarchy of intermolecular interactions in molecular crystal structures by using tunable halogen bonds

A family of 16 isomolecular salts (3-XpyH)(2)[MX'(4)] (3-XpyH=3-halopyridinium; M=Co, Zn; X=(F), Cl, Br, (I); X'=Cl, Br, I) each containing rigid organic cations and tetrahedral halometallate anions has been prepared and characterized by X-ray single crystal and/or powder diffraction. Their crystal structures reflect the competition and cooperation between non-covalent interactions: N-H center dot center dot center dot X'-M hydrogen bonds, C-X center dot center dot center dot X'-M halogen bonds and pi-pi stacking. The latter are essentially unchanged in strength across the series, but both halogen bonds and hydrogen bonds are modified in strength upon changing the halogens involved. Changing the organic halogen (X) from F to I strengthens the C-X center dot center dot center dot X'-M halogen bonds, whereas an analogous change of the inorganic halogen (X') weakens both halogen bonds and N-H center dot center dot center dot X'-M hydrogen bonds. By so tuning the strength of the putative halogen bonds from repulsive to weak to moderately strong attractive interactions, the hierarchy of the interactions has been modified rationally leading to systematic changes in crystal packing. Three classes of crystal structure are obtained. In type A (C-F center dot center dot center dot X'-M) halogen bonds are absent. The structure is directed by N-H center dot center dot center dot X'-M hydrogen bonds and pi-stacking interactions. In type B structures, involving small organic halogens (X) and large inorganic halogens (X'), long (weak) C-X center dot center dot center dot X'-M interactions are observed with type I halogen-halogen interaction geometries (C-X center dot center dot center dot X' approximate to X center dot center dot center dot X'-M approximate to 155 degrees), but hydrogen bonds still dominate. Thus, minor but quite significant perturbations from the type A structure arise. In type C, involving larger organic halogens (X) and smaller inorganic halogens (X'), stronger halogen bonds are formed with a type II halogen-halogen interaction geometry (C-X center dot center dot center dot X' approximate to 180 degrees; X center dot center dot center dot X'-M approximate to 110 degrees) that is electrostatically attractive. The halogen bonds play a major role alongside hydrogen bonds in directing the type C structures, which as a result are quite different from type A and B.

Carbon (C-13) and nitrogen (N-15) translocation in a maize-Striga hermonthica association

The translocation of C and N in a maize-Striga hermonthica association was investigated at three rates of nitrogen application in a glasshouse experiment. The objectives were to measure the transfer of C and N from maize to S. hermonthica and to determine whether the amount of N in the growing medium affected the proportions of C and N transferred. Young plants of maize were labelled in a (CO2)-C-13 atmosphere and leaf tips were immersed in ((NH4)-N-15)(2)SO4 Solution. The Striga x N interaction was not significant for any of the responses measured. Total dry matter for infected maize was significantly smaller than for uninfected maize from 43 to 99 days after planting, but N application increased total dry matter at all sampling times. Infected maize plants partitioned 39-45 % of their total dry matter to the roots compared with 28-31 % for Uninfected maize. Dry matter of S. hermonthica was not affected by the rate of N applied. S. hermonthica derived 100 % of its carbon from maize before emergence, decreasing to 22-59 % thereafter; the corresponding values for nitrogen were up to 59 % pre-emergence and Lip to 100 % after emergence. The relative proportions of nitrogen depleted from the host (up to 10 %) were greater than those of carbon (maximum 1.2 %) at all times of sampling after emergence of the parasite. The results show that the parasite was more dependent on the host for nitrogen than for carbon.

Predicted soil organic carbon stocks and changes in Jordan between 2000 and 2030 made using the GEFSOC modelling system

Estimates of soil organic carbon (SOC) stocks and changes under different land use systems can help determine vulnerability to land degradation. Such information is important for countries in and areas with high susceptibility to desertification. SOC stocks, and predicted changes between 2000 and 2030, were determined at the national scale for Jordan using The Global Environment Facility Soil Organic Carbon (GEFSOC) Modelling System. For the purpose of this study, Jordan was divided into three natural regions (The Jordan Valley, the Uplands and the Badia) and three developmental regions (North, Middle and South). Based on this division, Jordan was divided into five zones (based on the dominant land use): the Jordan Valley, the North Uplands, the Middle Uplands, the South Uplands and the Badia. This information was merged using GIS, along with a map of rainfall isohyets, to produce a map with 498 polygons. Each of these was given a unique ID, a land management unit identifier and was characterized in terms of its dominant soil type. Historical land use data, current land use and future land use change scenarios were also assembled, forming major inputs of the modelling system. The GEFSOC Modelling System was then run to produce C stocks in Jordan for the years 1990, 2000 and 2030. The results were compared with conventional methods of estimating carbon stocks, such as the mapping based SOTER method. The results of these comparisons showed that the model runs are acceptable, taking into consideration the limited availability of long-term experimental soil data that can be used to validate them. The main findings of this research show that between 2000 and 2030, SOC may increase in heavily used areas under irrigation and will likely decrease in grazed rangelands that cover most of Jordan giving an overall decrease in total SOC over time if the land is indeed used under the estimated forms of land use. (C) 2007 Elsevier B.V. All rights reserved.

Cropping systems, carbon sequestration and erosion in Brazil, a review

Soils represent a large carbon pool, approximately 1500 Gt, which is equivalent to almost three times the quantity stored in terrestrial biomass and twice the amount stored in the atmosphere. Any modification of land use or land management can induce variations in soil carbon stocks, even in agricultural systems that are perceived to be in a steady state. Tillage practices often induce soil aerobic conditions that are favourable to microbial activity and may lead to a degradation of soil structure. As a result, mineralisation of soil organic matter increases in the long term. The adoption of no-tillage systems and the maintenance of a permanent vegetation cover using Direct seeding Mulch-based Cropping system or DMC, may increase carbon levels in the topsoil. In Brazil, no-tillage practices (mainly DMC), were introduced approximately 30 years ago in the south in the Parana state, primarily as a means of reducing erosion. Subsequently, research has begun to study the management of the crop waste products and their effects on soil fertility, either in terms of phosphorus management, as a means of controlling soil acidity, or determining how manures can be applied in a more localised manner. The spread of no-till in Brazil has involved a large amount of extension work. The area under no-tillage is still increasing in the centre and north of the country and currently occupies ca. 20 million hectares, covering a diversity of environmental conditions, cropping systems and management practices. Most studies of Brazilian soils give rates of carbon storage in the top 40 cm of the soil of 0.4 to 1.7 t C ha(-1) per year, with the highest rates in the Cerrado region. However, caution must be taken when analysing DMC systems in terms of carbon sequestration. Comparisons should include changes in trace gas fluxes and should not be limited to a consideration of carbon storage in the soil alone if the full implications for global warming are to be assessed.

Modelled soil organic carbon stocks and changes in the Indo-Gangetic Plains, India from 1980 to 2030

The Global Environment Facility co-financed Soil Organic Carbon (GEFSOC) Project developed a comprehensive modelling system for predicting soil organic carbon (SOC) stocks and changes over time. This research is an effort to predict SOC stocks and changes for the Indian, Indo-Gangetic Plains (IGP), an area with a predominantly rice (Oryza sativa) - wheat (Triticum aestivum) cropping system, using the GEFSOC Modelling System and to compare output with stocks generated using mapping approaches based on soil survey data. The GEFSOC Modelling System predicts an estimated SOC stock for the IGP, India of 1.27, 1.32 and 1.27 Pg for 1990, 2000 and 2030, respectively, in the top 20 cm of soil. The SOC stock using a mapping approach based on soil survey data was 0.66 and 0.88 Pg for 1980 and 2000, respectively. The SOC stock estimated using the GEFSOC Modelling System is higher than the stock estimated using the mapping approach. This is due to the fact that while the GEFSOC System accounts for variation in crop input data (crop management), the soil mapping approach only considers regional variation in soil texture and wetness. The trend of overall change in the modelled SOC stock estimates shows that the IGP, India may have reached an equilibrium following 30-40 years of the Green Revolution. This can be seen in the SOC stock change rates. Various different estimation methods show SOC stocks of 0.57-1.44 Pg C for the study area. The trend of overall change in C stock assessed from the soil survey data indicates that the soils of the IGP, India may store a projected 1.1 Pg of C in 2030. (C) 2007 Elsevier B.V. All rights reserved.

Liming upland grassland: the effects on earthworm communities and the chemical characteristics of carbon in casts

Different earthworm species have different tolerances of acid soil conditions, and the application of lime to upland grassland to improve the grazing quality may therefore alter the size and diversity of the earthworm community. Altering soil properties may also affect the chemical characteristics of organic C in earthworm casts. We surveyed the earthworm community of an upland grassland in southern Scotland at the outset of annual lime applications, and after 3 years, and used C-13 nuclear magnetic resonance (NMR) spectroscopy to assess the distribution of C between different functional groups in the organic matter. In addition, soil was incubated for 8 weeks with several earthworm species in the presence or absence of lime, and the earthworm casts were subsequently analysed by C-13 NMR spectroscopy. Liming did not significantly affect earthworm abundance or species diversity, but it did affect the chemical composition of the casts. Casts from earthworms incubated in unlimed soil had greater ratios of alkyl-C to O-alkyl-C, indicative of more decomposed, recalcitrant C, and spectra from litter-feeding species had the greatest intensities of O-alkyl-C signals. In limed soil, the largest O-alkyl-C signal intensities were not restricted to litter-feeding species, indicating an increase in the quality of organic matter ingested by geophagous species.

Predicted soil organic carbon stocks and changes in the Brazilian Amazon between 2000 and 2030

Currently we have little understanding of the impacts of land use change on soil C stocks in the Brazilian Amazon. Such information is needed to determine impacts'6n the global C cycle and the sustainability of agricultural systems that are replacing native forest. The aim of this study was to predict soil carbon stocks and changes in the Brazilian Amazon during the period between 2000 and 2030, using the GEFSOC soil carbon (C) modelling system. In order to do so, we devised current and future land use scenarios for the Brazilian Amazon, taking into account: (i) deforestation, rates from the past three decades, (ii) census data on land use from 1940 to 2000, including the expansion and intensification of agriculture in the region, (iii) available information on management practices, primarily related to well managed pasture versus degraded pasture and conventional systems versus no-tillage systems for soybean (Glycine max) and (iv) FAO predictions on agricultural land use and land use changes for the years 2015 and 2030. The land use scenarios were integrated with spatially explicit soils data (SOTER database), climate, potential natural vegetation and land management units using the recently developed GEFSOC soil C modelling system. Results are presented in map, table and graph form for the entire Brazilian Amazon for the current situation (1990 and 2000) and the future (2015 and 2030). Results include soil organic C (SOC) stocks and SOC stock change rates estimated by three methods: (i) the Century ecosystem model, (ii) the Rothamsted C model and (iii) the intergovernmental panel on climate change (IPCC) method for assessing soil C at regional scale. In addition, we show estimated values of above and belowground biomass for native vegetation, pasture and soybean. The results on regional SOC stocks compare reasonably well with those based on mapping approaches. The GEFSOC system provided a means of efficiently handling complex interactions among biotic-edapho-climatic conditions (> 363,000 combinations) in a very large area (similar to 500 Mha) such as the Brazilian Amazon. All of the methods used showed a decline in SOC stock for the period studied; Century and RothC simulated values for 2030 being about 7% lower than those in 1990. Values from Century and RothC (30,430 and 25,000 Tg for the 0-20 cm layer for the Brazilian Amazon region were higher than those obtained from the IPCC system (23,400 Tg in the 0-30 cm layer). Finally; our results can help understand the major biogeochemical cycles that influence soil fertility and help devise management strategies that enhance the sustainability of these areas and thus slow further deforestation. (C) 2007 Elsevier B.V. All rights reserved.