Decomposition and phosphorus release from organic residues as affected by residue quality and added inorganic phosphorus

The combined use of organic residue and inorganic fertiliser-phosphorus (P) is appropriate in meeting both the short and long-term P requirement of crops. To assess the influence of added inorganic fertiliser-P on the processes of decomposition and P release from the residue and the relationships with quality, prunings of Gliricidia sepium, Leucaena leucocephela, Senna siamea, Acacia mangium and Paraserienthus falcataria were incubated without and with added inorganic fertiliser-P for 56 days. Soil was added only as inoculum. Decomposition rate and amounts of acid extractable-P (P release) were in the same order: G. sepium > S. siamea > L. leucocepheta > P falcataria > A. mangium. Unlike the other residues, A. mangium released no P despite the loss of half its mass during the 8 weeks of incubation. The residue P content correlated with P release. However, decomposition rate did not correlate with residue P content but with the lignin, polyphenol and cellulose content, and ratios to P. These ratios were negatively correlated with P release suggesting that lignin and polyphenol contents influence P release more when the residue-P content is low. Results suggest that rate of decomposition influences the release of P. The critical residue P content for P release was estimated to be 0.12% < P < 0.19%. Added P had no effect on decomposition and P release from the residues.

Decomposition in soil and chemical characteristics of pollen

The input to soils made by pollen and its subsequent mineralization has rarely been investigated from a soil microbiological point of view even though the small but significant quantities of C and N in pollen may make an important contribution to nutrient cycling. The relative resistance to decomposition of pollen exines (outer layers) has led to much of the focus of pollen in soil being on its preservation for archaeological and palaeo-ecological purposes. We have examined aspects of the chemical composition and decomposition of pollen from birch (Betula alba) and maize (Zea mays) in soil. The relatively large N contents, small C-to-N ratios and large water-soluble contents of pollen from both species indicated that they would be readily mineralized in soil. When added to soil and incubated at 16 degrees C an amount of C equivalent to 22-26% of the added pollen C was lost as CO2 within 22 days, with the Z. mays pollen decomposing faster. For B. alba pollen, the water-soluble fraction decomposed faster than the whole pollen and the insoluble fraction decomposed more slowly over 22 days. By contrast, there were no significant differences in the decomposition rates of the different fractions from Z. mays pollen. Solid-state C-13 nuclear magnetic resonance (NMR) revealed no gross chemical differences between the pollen of these two species, with strong resonances in the alkyl- and methyl-C region (0-45 p.p.m.) indicative of aliphatic compounds, the O-alkyl-C (60-90 p.p.m.) and the acetal- and ketal-C region (90-110 p.p.m.) indicative of polysaccharides, and the carbonyl-C region indicative of peptides and carboxylic acids. In addition, both pollens gave a small but distinct resonance at 55 p.p.m. attributed to N-alkyl-C. The resonances attributed to polysaccharides were lost completely or substantially reduced after decomposition.

Spin spaces and positive decomposition of linear maps on ordered Banach spaces

Spin factors and generalizations are used to revisit positive generation of B(E, F), where E and F are ordered Banach spaces. Interior points of B(E, F)+ are discussed and in many cases it is seen that positive generation of B(E, F) is controlled by spin structure in F when F is a JBW-algebra.

Influence of adsorption geometry in the heterogeneous enantioselective catalytic hydrogenation of a prototypical enone

Asymmetric catalysis is of paramount importance in organic synthesis and, in current practice, is achieved by means of homogeneous catalysts. The ability to catalyze such reactions heterogeneously would have a major impact both in the research laboratory and in the production of fine chemicals and pharmaceuticals, yet heterogeneous asymmetric hydrogenation of C═C bonds remains hardly explored. Very recently, we demonstrated how chiral ligands that anchor robustly to the surface of Pd nanoparticles promote asymmetric catalytic hydrogenation: ligand rigidity and stereochemistry emerged as key factors. Here, we address a complementary question: how does the enone reactant adsorb on the metal surface, and what implications does this have for the enantiodifferentiating interaction with the surface-tethered chiral modifiers? A reaction model is proposed, which correctly predicts the identity of the enantiomer experimentally observed in excess.

The impact of two arable field margin management schemes on litter decomposition

A primary objective of agri-environment schemes is the conservation of biodiversity; in addition to increasing the value of farmland for wildlife, these schemes also aim to restore natural ecosystem functioning. The management of scheme options can influence their value for delivering ecosystem services by modifying the composition of floral and faunal communities. This study examines the impact of an agri-environment scheme prescription on ecosystem functioning by testing the hypothesis that vegetation management influences decomposition rates in grassy arable field margins. The effects of two vegetation management practices in arable field margins - cutting and soil disturbance (scarification) - on litter decomposition were compared using a litterbag experimental approach in early April 2006. Bags had either small mesh designed to restrict access to soil macrofauna, or large mesh that would allow macrofauna to enter. Bags were positioned on the soil surface or inserted into the soil in cut and scarified margins, retrieved after 44, 103 and 250 days and the amount of litter mass remaining was calculated. Litter loss from the litterbags with large mesh was greater than from the small mesh bags, providing evidence that soil macrofauna accelerate rates of litter decomposition. In the large mesh bags, the proportion of litter remaining in bags above and belowground in the cut plots was similar, while in the scarified plots, there was significantly more litter left in the aboveground bags than in the belowground bags. This loss of balance between decomposition rates above and belowground in scarified margins may have implications for the development and maintenance of grassy arable field margins by influencing nutrient availability for plant communities. (C) 2008 Elsevier B.V. All rights reserved.

Phoretic mites associated with animal and human decomposition

Phoretic mites are likely the most abundant arthropods found on carcases and corpses. They outnumber their scavenger carriers in both number and diversity. Many phoretic mites travel on scavenger insects and are highly specific; they will arrive on a particular species of host and no other. Because of this, they may be useful as trace indicators of their carriers even when their carriers are absent. Phoretic mites can be valuable markers of time. They are usually found in a specialised transitional transport or dispersal stage, often moulting and transforming to adults shortly after arrival on a carcase or corpse. Many are characterised by faster development and generation cycles than their carriers. Humans are normally unaware, but we too carry mites; they are skin mites that are present in our clothes. More than 212 phoretic mite species associated with carcases have been reported in the literature. Among these, mites belonging to the Mesostigmata form the dominant group, represented by 127 species with 25 phoretic mite species belonging to the family Parasitidae and 48 to the Macrochelidae. Most of these mesostigmatids are associated with particular species of flies or carrion beetles, though some are associated with small mammals arriving during the early stages of decomposition. During dry decay, members of the Astigmata are more frequently found; 52 species are phoretic on scavengers, and the majority of these travel on late-arriving scavengers such as hide beetles, skin beetles and moths. Several species of carrion beetles can visit a corpse simultaneously, and each may carry 1-10 species of phoretic mites. An informative diversity of phoretic mites may be found on a decaying carcass at any given time. The composition of the phoretic mite assemblage on a carcass might provide valuable information about the conditions of and time elapsed since death.

Glycogen phosphorylase inhibitors: a free energy perturbation analysis of glucopyranose spirohydantoin analogues

GP catalyzes the phosphorylation of glycogen to Glc-1-P. Because of its fundamental role in the metabolism of glycogen, GP has been the target for a systematic structure-assisted design of inhibitory compounds, which could be of value in the therapeutic treatment of type 2 diabetes mellitus. The most potent catalytic-site inhibitor of GP identified to date is spirohydantoin of glucopyranose (hydan). In this work, we employ MD free energy simulations to calculate the relative binding affinities for GP of hydan and two spirohydantoin analogues, methyl-hydan and n-hydan, in which a hydrogen atom is replaced by a methyl- or amino group, respectively. The results are compared with the experimental relative affinities of these ligands, estimated by kinetic measurements of the ligand inhibition constants. The calculated binding affinity for methyl-hydan (relative to hydan) is 3.75 +/- 1.4 kcal/mol, in excellent agreement with the experimental value (3.6 +/- 0.2 kcal/mol). For n-hydan, the calculated value is 1.0 +/- 1.1 kcal/mol, somewhat smaller than the experimental result (2.3 +/- 0.1 kcal/mol). A free energy decomposition analysis shows that hydan makes optimum interactions with protein residues and specific water molecules in the catalytic site. In the other two ligands, structural perturbations of the active site by the additional methyl- or amino group reduce the corresponding binding affinities. The computed binding free energies are sensitive to the preference of a specific water molecule for two well-defined positions in the catalytic site. The behavior of this water is analyzed in detail, and the free energy profile for the translocation of the water between the two positions is evaluated. The results provide insights into the role of water molecules in modulating ligand binding affinities. A comparison of the interactions between a set of ligands and their surrounding groups in X-ray structures is often used in the interpretation of binding free energy differences and in guiding the design of new ligands. For the systems in this work, such an approach fails to estimate the order of relative binding strengths, in contrast to the rigorous free energy treatment.

Photocatalytic degradation of humic acid in saline waters. Part 1. Artificial seawater: influence of TiO2, temperature, pH, and air-flow

We report the first systematic study on the photocatalytic oxidation of humic acid (HA) in artificial seawater (ASW). TiO2 (Degussa P25) dispersions were used as the catalyst with irradiation from a medium-pressure mercury lamp. The optimum quantity of catalyst was found to be between 2 and 2.5 g l(-1); whiled the decomposition was fastest at low pH values (pH 4.5 in the range examined), and the optimum air-flow, using an immersion well reactor with a capacity of 400 ml, was 850 ml min(-1). Reactivity increased with air-flow up to this figure, above which foaming prevented operation of the reactor. Using pure. oxygen, an optimal flow rate was observed at 300 nil min(-1), above which reactivity remains essentially constant. Following treatment for 1 h, low-salinity water (2700 mg l(-1)) was completely mineralised, whereas ASW (46000 mg l(-1)) had traces of HA remaining. These effects are interpreted and kinetic data presented. To avoid problems of precipitation due to change of ionic strength humic substances were prepared directly in ASW, and the effects of ASW on catalyst suspension and precipitation have been taken into account. The Langmuir-Hinshelwood kinetic model has been shown to be followed only approximately for the catalytic oxidation of HA in ASW. The activation energy for the reaction derived from an Arrhenius treatment was 17 ( +/-0.6) kJ mol(-1). (C) 2003 Elsevier Science Ltd. All rights reserved.

Chemoselective catalytic hydrogenation of acrolein on Ag(111): effect of molecular orientation on reaction selectivity

The adsorption and hydrogenation of acrolein on the Ag(111) surface has been investigated by high resolution synchrotron XPS, NEXAFS, and temperature programmed reaction. The molecule adsorbs intact at all coverages and its adsorption geometry is critically important in determining chemoselectivity toward the formation of allyl alcohol, the desired but thermodynamically disfavored product. In the absence of hydrogen adatoms (H(a)), acrolein lies almost parallel to the metal surface; high coverages force the C=C bond to tilt markedly, likely rendering it less vulnerable toward reaction with hydrogen adatoms. Reaction with coadsorbed H(a) yields allyl alcohol, propionaldehyde, and propanol, consistent with the behavior of practical dispersed Ag catalysts operated at atmospheric pressure: formation of all three hydrogenation products is surface reaction rate limited. Overall chemoselectivity is strongly influenced by secondary reactions of allyl alcohol. At low H(a) coverages, the C=C bond in the newly formed allyl alcohol molecule is strongly tilted with respect to the surface, rendering it immune to attack by H(a) and leading to desorption of the unsaturated alcohol. In contrast with this, at high H(a) coverages, the C=C bond in allyl alcohol lies almost parallel to the surface, undergoes hydrogenation by H(a), and the saturated alcohol (propanol) desorbs.

Oxo-rhenium(V) complexes with bidentate phosphine ligands: synthesis, crystal structure and catalytic potentiality in epoxidation of olefins using hydrogen peroxide activated bicarbonate as oxidant

Two oxorhenium(V) complexes with bidentate phosphine ligands were synthesized and isolated as [ReOCl3(dppm)] 1 and [ReOCl3(dppp)] 2 [where dppm = 1,1-bis(diphenylphosphino) methane and dppp = 1.3-bis(diphenylphosphino) propanel. Complex 2 was structurally characterized. Both the complexes were used as catalysts in the epoxidation of olefins using NaHCO3 as co-catalyst and H2O2 as terminal oxidant. (c) 2008 Elsevier B.V. All rights reserved.

Catalytic oxidation of alcohols using molecular oxygen mediated by poly(ethylene glycol)-supported nitroxyl radicals

The selective catalytic oxidation of alcohols over a mixture of copper(l) chloride and a number of linear 'linker-less' or 'branched' poly(ethylene glycol)-supported nitroxyl radicals of the 2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPO) family as a catalyst system has been investigated in the presence of molecular oxygen in a batch reactor. It is found that the activity profile of the polymer-supported nitroxyl radicals is in good agreement with that of low-molecular weight nitroxyl catalysts, for example, allylic and benzylic alcohols are oxidised faster than aliphatic alcohols. The oxidations can be tuned to be highly selective such that aldehydes are the only oxidation products observed in the oxidation of primary alcohols and the oxidations of secondary alcohols yield the corresponding ketones. A strong structural effect of the polymeric nitroxyl species on catalytic activity that is dependent upon their spatial orientation of the nitroxyl radicals is particularly noted. The new soluble macromolecular catalysts can be recovered readily from the reaction mixture by solvent precipitation and filtration. In addition, the recycled catalysts demonstrate a similar selectivity with only a small decrease in activity compared to the fresh catalyst even after five repetitive cycles. (c) 2005 Elsevier B.V. All rights reserved.

Tin and tin-titanium as catalyst components for reversible hydrogen storage of sodium aluminium hydride

This paper is concerned with the effects of adding tin and/or titanium dopant to sodium aluminium hydride for both dehydrogenation and re-hydrogenation reactions during their reversible storage of molecular hydrogen. Temperature programmed decomposition (TPD) measurements show that the dehydrogenation kinetics of NaAlH4 are significantly enhanced upon doping the material with 2 mol% of tributyltin hydride, Sn(Bu)(3)H but the tin catalyst dopant is shown to be inferior than titanium. On the other hand, in this preliminary work, a significant synergetic catalytic effect is clearly revealed in material co-doped with both titanium and tin catalysts which shows the highest reversible rates of dehydrogenation and re-hydrogenation (after their hydrogen depletion). The re-hydrogenation rates of depleted Sn/Ti/NaAlH4 evaluated at both 9.5 and 140 bars hydrogen are also found to be favourable compared to the Ti/NaAlH4, which clearly suggest the importance of the catalyst choice. Basing on these results some mechanistic insights for the catalytic reversible dehydrogenation and re-hydrogenation processes of Sn/Ti/NaAlH4 are therefore made. (C) 2006 Elsevier Ltd. All rights reserved.