The influence of winter oilseed rape (Brassica napus ssp oleifera var. biennis) canopy size on grass weed growth and grass weed seed return

Four experiments conducted over three seasons (2002-05) at the Crops Research Unit, University of Reading, investigated effects of canopy management of autumn sown oilseed rape (Brassica napus L. ssp. oleifera var. biennis (DC.) Metzg.) on competition with grass weeds. Emphasis was placed on the effect of the crop on the weeds. Rape canopy size was manipulated using sowing date, seed rate and the application of autumn fertilizer. Lolium multiflorum Lam., L. x boucheanum Kunth and Alopecurus myosuroides Huds. were sown as indicative grass weeds. The effects of sowing date, seed rate and autumn nitrogen on crop competitive ability were correlated with rape biomass and fractional interception of photosynthetically active radiation (PAR) by the rape floral layer, to the extent that by spring there was good evidence of crop: weed replacement. An increase in seed rate up to the highest plant densities tested increased both rape biomass and competitiveness, e.g. in 2002/3, L. multiflorum head density was reduced from 539 to 245 heads/m(2) and spikelet density from 13 170 to 5960 spikelets/m(2) when rape plant density was increased from 16 to 81 plants/m(2). Spikelets/head of Lolium spp. was little affected by rape seed rate, but the length of heads of A. myosuroides was reduced by 9 % when plant density was increased from 29-51 plants/m(2). Autumn nitrogen increased rape biomass and reduced L. multiflorum head density (415 and 336 heads/m(2) without and with autumn nitrogen, respectively) and spikelet density (9990 and 8220 spikelets/m(2) without and with autumn nitrogen, respectively). The number of spikelets/head was not significantly affected by autumn nitrogen. Early sowing could increase biomass and competitiveness, but poor crop establishment sometimes overrode the effect. Where crop and weed establishment was similar for both sowing dates, a 2-week delay (i.e. early September to mid-September) increased L. multiflorum head density from 226 to 633 heads/m(2) and spikelet density from 5780 to 15 060 spikelets/m(2).

The influence of winter oilseed rape (Brassica napus ssp oleifera var. biennis) cultivar and grass genotype on the competitive balance between crop and grass weeds

Three experiments conducted over two years (2002-04) at the Crops Research Unit, University of Reading, investigated competition between autumn sown oilseed rape cultivars (Brassica napus L. ssp. oleifera var. biennis (DC.) Metzg.) and Lolium multiflorum Lam., L. x boucheanum Kunth and Alopecurus myosuroides Huds., sown as indicative grass weeds. Rape cultivar (cv.) had a substantial effect on grass weed seed return. Over the six cultivars tested, L. multiflorum spikelet production ranged from just under 400 spikelets/m(2) in the presence of cv. Winner to nearly 5800 in competition with cv. Lutin. Cultivar competitiveness was associated with high biomass, large dense floral layers and early stem extension. There was some evidence of differential competitive tolerance between rape cultivars. The results suggested that rape cultivars could be screened for competitiveness by measuring floral layer interception of photosynthetic active radiation. L. x boucheanum cultivars varied in ability to compete with rape. In the absence of inter-specific competition, spikelet density was similar for Aberecho and Polly (circa 31000 spikelets/m(2)) but when grown with rape Polly outyielded Aberecho (i.e. 12 090 and 7990 spikelets/m(2) respectively).

Metallothionein I and II gene expression as a response to metal contamination in bank vole Clethrionomys glareolus

The expression of two metallothionein genes (Mt-I and Mt-II) in the liver, kidney, and gonad of bank voles collected at four metal-contaminated sites (Cd, Zn, Pb, and Fe) were measured using the quantitative real-time PCR method (QPCR). Relative Mt gene expression was calculated by applying a normalization factor (NF) using the expression of two housekeeping genes, ribosomal 18S and beta-actin. Relative Mt expression in tissues of animals from contaminated sites was up to 54.8-fold higher than those from the reference site for Mt-I and up to 91.6-fold higher for Mt-II. Mt-II gene expression in the livers of bank voles from contaminated sites was higher than Mt-I gene expression. Inversely, Mt-II expression in the kidneys of voles was lower than Mt-I expression. Positive correlations between cadmium levels in the tissues and Mt-I were obtained in all studied tissues. Zinc, which undergoes homeostatic regulation, correlated positively with both Mt-I and Mt-II gene expression only in the kidney. Results showed that animals living in chronically contaminated environments intensively activate detoxifying mechanisms such as metallothionein expression. This is the first time that QPCR techniques to measure MT gene expression have been applied to assess the impact of environmental metal pollution on field collected bank voles.

Combining competition from Lolium perenne and an insect-fungus combination to control Rumex obtusifolius seedlings

Although adult Rumex obtusifolius are problematic weeds, their seedlings are poor competitors against Lolium perenne, particularly in established swards. We investigated the possibility of using this weakness to augment control of R. obtusifolius seedlings with combinations of Gastrophysa viridula (Coleoptera: Chrysomelidae) and the rust fungus Uromyces rumicis. Rumex obtusifolius seedlings were grown in competition with L. perenne sown at different rates and times after R. obtusifolius: they competed successfully with L. perenne when sown 21 days before the grass. Sowing both species at the same time resulted in a dominant grass sward, with R. obtusifolius becoming dominant when sown 42 days prior to L. perenne. Grass sowing rate had no effect on R. obtusifolius growth or biomass. A second experiment investigated how competition from L. perenne sown 21 days after R. obtusifolius combined with damage from G. viridula and/or U. rumicis (applied at either the 3-4- or 10-13-leaf stage, or at both stages) affected the growth and final biomass of R. obtusifolius. Beetle grazing at the latter leaf stage was the only treatment that reduced R. obtusifolius biomass, although rust infection at the earlier application led to an increase in shoot and root weight. The results are discussed in terms of the potential for use of these agents in the field.

Complete filling of zeolite frameworks with polyalkynes formed in situ by transition-metal ion catalysts

We report the use of transition-metal-exchanged zeolites as media for the catalytic formation and encapsulation of both polyethyne and polypropyne, and computer modeling studies on the composites so formed. Alkyne gas was absorbed into the pores of zeolite Y (Faujasite) exchanged with transition-metal cations [Fe(II), Co(II), Cu(II), Ni(II), and Zn(II)]. Ni(II) and Zn(II) were found to be the most efficient for the production of poly-ynes. These cations were also found to be effective in polymer generation when exchanged in zeolites mordenite and beta. The resulting powdered samples were characterized by FTIR, Raman, diffuse reflectance electronic spectroscopy, TEM, and elemental analysis, revealing, nearly complete loading of the zeolite channels for the majority of the samples. Based on the experimental carbon content, we have derived the percentage of channel filling, and the proportion of the channels containing a single polymer chain for mordenite. Experimentally, the channels for Y are close to complete filling for polyethyne (PE) and polypropyne (PP), and this is also true for polyethyne in mordenite. Computer modeling studies using Cerius2 show that the channels of mordenite can only accept a single polymer chain of PP, in which case these channels are also completely filled.

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.

Synthesis and catalytic epoxidation potentiality of oxodiperoxo molybdenum(VI) complexes with pyridine-2-carboxaldoxime and pyridine-2-carboxylate: the crystal structure of PMePh3[MoO(O-2)(2)(PyCO)]

[MoO(O-2)(2)(PyCOXH)(H2O)] and PMePh3[MoO(O-2)(2)(PyCO)] (PyCOXH = Pyridine-2-carboxaldoxime and PyCOH = Pyridine-2-carboxylic acid) have been synthesized. Both complexes have been characterized by physico-chemical and spectroscopic methods; in addition, the carboxylate complex has been structurally characterized by X-ray crystallography. The carboxylate complex is a more efficient catalyst than the oxime complex for epoxidation of olefins and shows excellent catalytic activity for the substrates: cyclooctene, cinnamyl alcohol, allyl alcohol and 1-hexene.

Peroxides in ordered nanoporous silicas: clean alternatives to transition metal oxidants for the removal of toxic gases

Ordered nano-structured MCM-48 silica containing sodium peroxydisulfate is a novel, highly effective material for the decomposition of HCN under ambient conditions.

Peroxydisulfate in MCM-48 silicas: powerful and clean materials for the removal of toxic gases

Sodium persulfate introduced into ordered MCM-48 silicas is described. The resulting materials are compared with existing activated carbon-based systems and MCM-48 containing transition metals such as Cu(II) and Cr(VI) for the decomposition of hydrogen cyanide and cyanogen. MCM-48 materials containing sodium persulfate alone improve on the protection offered by benchmark activated carbon systems and MCM-48 materials containing Cu(II) and Cr(VI), without the health risks associated with these metal ions.

Partial aerial oxidation of nonpolar alcohols over Teflon-modified noble metal catalysts in supercritical carbon dioxide

We have reported earlier that modification of commercial graphite Pt-supported catalysts with Teflon fluorinated polymeric coating of a very strong hydrophobic nature can significantly improve catalytic activity for aerial oxidation of water-insoluble alcohols such as anthracene methanol in supercritical carbon dioxide (scCO(2)). Thus, this paper presents some further characterization of these new catalyst materials and the working fluid phase during the catalysis. Using the same Teflon-modified metal catalysts, this paper addresses the oxidation of another water-insoluble alcohol molecule, m-hydrobenzoin in scCO(2). It is found that conversion and product distribution of this diol oxidation critically depend on the temperature and pressure of the scCO(2) used, which suggest the remarkable solvent properties of the scCO(2) under these unconventional oxidation conditions. (C) 2004 Elsevier Inc. All rights reserved.

Deprotection, tethering, and activation of a one-legged metalloporphyrin on a chemically active metal surface: NEXAFS, Synchrotron XPS, and STM study of [SAc]P-Mn(III)Cl on Ag(100)

The structural and reactive properties of the acetyl-protected "one-legged" manganese porphyrin [SAc]P-Mn(III)Cl on Ag(100) have been studied by NEXAFS, synchrotron XPS and STM Spontaneous surface-mediated deprotection occurs at 300 K accompanied by spreading of the resulting thio-tethered porphyrin across the metal surface Loss of the axial chlorine ligand occurs at 498 K, without any demetalation of the macrocycle, leaving the Mn center in a low co-ordination state At low coverages the macrocycle is markedly tilted toward the silver surface, as is the phenyl group that forms part of the tethering "leg". In the monolayer region a striking transition occurs whereby the molecule rolls over, preserving the tilt angle of the phenyl group, strongly increasing that of the macrocycle, decreasing the apparent height of the molecule and decreasing its footprint, thus enabling closer packing These findings are in marked contrast with those previously reported for the corresponding more rigidly bound four-legged porphyrin [Turner, M., Vaughan, O. P. H., Kyriakou, G., Watson, D. J., Scherer, L. J; Davidson, G J. E, Sanders, J. K. M.; Lambert, R. M J. Am. Chem Soc 2009, 131, 1910] suggesting that the physicochemical :)properties and potential applications of these versatile systems should be strongly dependent on the mode of tethering to the surface.

Deprotection, tethering, and activation of a catalytically active metalloporphyrin to a chemically active metal surface: [SAc](4)P-Mn(III)Cl on Ag(100)

The adsorption and subsequent thermal chemistry of the acetyl-protected manganese porphyrin, [SA(C)](4)P-Mn(III)Cl on Ag(100) have been studied by high resolution XPS and temperature-programmed desorption. The deprotection event, leading to formation of the covalently bound thioporphyrin, has been characterized and the conditions necessary for removal of the axial chlorine ligand have been determined, thus establishing a methodology for creating tethered activated species that could serve as catalytic sites for delicate oxidation reactions. Surface-mediated acetyl deprotection occurs at 298 K, at which temperature porphyrin diffusion is limited. At temperatures above similar to 425 K porphyrin desorption, diffusion and deprotection occur and at >470 K the axial chlorine is removed.

Engineering Pt in ceria for a maximum metal-support interaction in catalysis

Conventional supported metal catalysts are metal nanoparticles deposited on high surface area oxide supports with a poorly defined metal−support interface. Typically, the traditionally prepared Pt/ceria catalyzes both methanation (H2/CO to CH4) and water−gas shift (CO/H2O to CO2/H2) reactions. By using simple nanochemistry techniques, we show for the first time that Pt or PtAu metal can be created inside each CeO2 particle with tailored dimensions. The encapsulated metal is shown to interact with the thin CeO2 overlayer in each single particle in an optimum geometry to create a unique interface, giving high activity and excellent selectivity for the water−gas shift reaction, but is totally inert for methanation. Thus, this work clearly demonstrates the significance of nanoengineering of a single catalyst particle by a bottom-up construction approach in modern catalyst design which could enable exploitation of catalyst site differentiation, leading to new catalytic properties.

One-step catalytic cyclohexane oxidation to adipic acid using molecular oxygen

Using combination of Mn-Co transition metal species with N-hydroxyphthalimide as a catalyst for one-step oxidation of cyclohexane with molecular oxygen in acetic acid at 353 K can give more than 95% selectivity towards oxygenated products with adipic acid as a major product at a high conversion (ca. 78%). A turnover number of 74 for this partial oxidation are also recorded.

Aerogel-coated metal nanoparticle colloids as novel entities for the synthesis of defined supported metal catalysts

Nanometer metal particles of tailored size (3-5 nm) and composition prepared via inverse microemulsion were encapsulated by ultrathin coatings (<2.5 nm) of inorganic porous aerogels covered with surface -OH groups. These composite materials formed metastable colloids in solvent(s), and the organic surfactant molecules were subsequently removed without leading to aggregation (the ethanolic colloid solution was shown to be stable against flocculation for at least weeks). We demonstrate that the totally inorganic-based composite colloids, after the removal of surfactant, can be anchored to conventional solid supports (gamma-alumina, carbons) upon mixing. Application of a high temperature resulted in the formation of strong covalent linkages between the colloids and the support because of the condensation of surface groups at the interface. Detailed characterizations (X-ray diffraction (XRD), pore analysis, transmission electron microscopy (TEM), CO chemisorption) and catalytic testing (butane combustion) showed that there was no significant metal aggregation from the fine metal particles individually coated with porous aerogel oxide. Most of these metal sites on the coated nanoparticles with and without support are fully accessible by small molecules hence giving extremely active metal catalysts. Thus, the product and technology described may be suitable to synthesize these precursor entities of defined metal sizes (as inks) for wash coat/impregnation applications in catalysis. The advantages of developing inorganic nanocomposite chemical precursors are also discussed.