Sonogashira coupling on an extended gold surface in vacuo: reaction of phenylacetylene with iodobenzene on Au(111)

Temperature-programmed reaction measurements supported by scanning tunneling microscopy have shown that phenylacetylene and iodobenzene react on smooth Au(111) under vacuum conditions to yield biphenyl and diphenyldiacetylene, the result of homocoupling of the reactant molecules. They also produce diphenylacetylene, the result of Sonogashira cross-coupling, prototypical of a class of reactions that are of paramount importance in synthetic organic chemistry and whose mechanism remains controversial. Roughened Au(111) is completely inert toward all three reactions, indicating that the availability of crystallographically well-defined adsorption sites is crucially important. High-resolution X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy show that the reactants are initially present as intact, essentially flat-lying molecules and that the temperature threshold for Sonogashira coupling coincides with that for C−I bond scission in the iodobenzene reactant. The fractional-order kinetics and low temperature associated with desorption of the Sonogashira product suggest that the reaction occurs at the boundaries of islands of adsorbed reactants and that its appearance in the gas phase is rate-limited by the surface reaction. These findings demonstrate unambiguously and for the first time that this heterogeneous cross-coupling chemistry is an intrinsic property of extended, metallic pure gold surfaces: no other species, including solvent molecules, basic or charged (ionic) species are necessary to mediate the process.

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 importance of sward architectural complexity in structuring predatory and phytophagous invertebrate assemblages

1. Although the importance of plant community assemblages in structuring invertebrate assemblages is well known, the role that architectural complexity plays is less well understood. In particular, direct empirical data for a range of invertebrate taxa showing how functional groups respond to plant architecture is largely absent from the literature. 2. The significance of sward architectural complexity in determining the species richness of predatory and phytophagous functional groups of spiders, beetles, and true bugs, sampled from 135 field margin plots over 2 years was tested. The present study compares the relative importance of sward architectural complexity to that of plant community assemblage. 3. Sward architectural complexity was found to be a determinant of species richness for all phytophagous and predatory functional groups. When individual species responses were investigated, 62.5% of the spider and beetle species, and 50.0% of the true bugs responded to sward architectural complexity. 4. Interactions between sward architectural complexity and plant community assemblage indicate that the number of invertebrate species supported by the plant community alone could be increased by modification of sward architecture. Management practices could therefore play a key role in diversifying the architectural structure of existing floral assemblages for the benefit of invertebrate assemblages. 5. The contrasting effects of sward architecture on invertebrate functional groups characterised by either direct (phytophagous species) or indirect (predatory species) dependence on plant communities is discussed. It is suggested that for phytophagous taxa, plant community assemblage alone is likely to be insufficient to ensure successful species colonisation or persistence without appropriate development of sward architecture.

Parametric accelerated failure time models with random effects and an application to kidney transplant survival

Accelerated failure time models with a shared random component are described, and are used to evaluate the effect of explanatory factors and different transplant centres on survival times following kidney transplantation. Different combinations of the distribution of the random effects and baseline hazard function are considered and the fit of such models to the transplant data is critically assessed. A mixture model that combines short- and long-term components of a hazard function is then developed, which provides a more flexible model for the hazard function. The model can incorporate different explanatory variables and random effects in each component. The model is straightforward to fit using standard statistical software, and is shown to be a good fit to the transplant data. Copyright (C) 2004 John Wiley Sons, Ltd.

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.

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.

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.

Film-forming polymers containing in the main-chain dibenzo crown ethers with aliphatic (C-10-C-16), aliphatic-aromatic, or oxyindole spacers

Novel, linear, soluble, high-molecular-weight, film-forming polymers and copolymers in which main-chain crown ether units alternate with aliphatic (C-10-C-16) units have been obtained for the first time from aromatic electrophilic substitution reactions of crown ethers by aliphatic dicarboxylic acids followed by reduction of the carbonyl groups. The crown ether unit is dibenzo-18-crown-6, dibenzo-21-crown-7, dibenzo-24-crown-8, or dibenzo-30-crown-10; the aliphatic spacer is derived from a dicarboxylic acid (sebacic, 1,12-dodecanedicarboxylic, hexadecanedioic or 1,4-phenylenediacetic acids). The reactions were performed at 35 degrees C in a mixture of methanesulfonic acid (MSA) with phosphorus pentoxide, 12:1 (w/w), (Eaton's reagent). The carbonyl groups in the polyketones obtained were completely reduced to methylene linkages by treatment at room temperature with triethylsilane in a mixture of trifluoroacetic acid and dichloromethane. Polymers containing in the main chain crown ethers alternating with oxyindole fragments were prepared by one-pot condensation of crown ethers with isatin in a medium of Eaton's reagent. A possible reaction mechanism is suggested. According to IR and NMR analyses, the polyacylation reactions lead to the formation of isomeric (syn/anti-substituted) crown ether units in the main chain. The polymers obtained were soluble in the common organic solvents, and flexible transparent films could be cast from the solutions. DSC and X-ray studies of the polymers with "symmetrical" crown ethers reveal the presence of the endotherms corresponding to the supramolecular assemblies.

On the spectra of certain integro-differential-delay problems with applications in neurodynamics

We investigate the spectrum of certain integro-differential-delay equations (IDDEs) which arise naturally within spatially distributed, nonlocal, pattern formation problems. Our approach is based on the reformulation of the relevant dispersion relations with the use of the Lambert function. As a particular application of this approach, we consider the case of the Amari delay neural field equation which describes the local activity of a population of neurons taking into consideration the finite propagation speed of the electric signal. We show that if the kernel appearing in this equation is symmetric around some point a= 0 or consists of a sum of such terms, then the relevant dispersion relation yields spectra with an infinite number of branches, as opposed to finite sets of eigenvalues considered in previous works. Also, in earlier works the focus has been on the most rightward part of the spectrum and the possibility of an instability driven pattern formation. Here, we numerically survey the structure of the entire spectra and argue that a detailed knowledge of this structure is important within neurodynamical applications. Indeed, the Amari IDDE acts as a filter with the ability to recognise and respond whenever it is excited in such a way so as to resonate with one of its rightward modes, thereby amplifying such inputs and dampening others. Finally, we discuss how these results can be generalised to the case of systems of IDDEs.

The relationship between land–ccean surface temperature contrast and radiative forcing

Previous work has demonstrated that observed and modeled climates show a near-time-invariant ratio of mean land to mean ocean surface temperature change under transient and equilibrium global warming. This study confirms this in a range of atmospheric models coupled to perturbed sea surface temperatures (SSTs), slab (thermodynamics only) oceans, and a fully coupled ocean. Away from equilibrium, it is found that the atmospheric processes that maintain the ratio cause a land-to-ocean heat transport anomaly that can be approximated using a two-box energy balance model. When climate is forced by increasing atmospheric CO2 concentration, the heat transport anomaly moves heat from land to ocean, constraining the land to warm in step with the ocean surface, despite the small heat capacity of the land. The heat transport anomaly is strongly related to the top-of-atmosphere radiative flux imbalance, and hence it tends to a small value as equilibrium is approached. In contrast, when climate is forced by prescribing changes in SSTs, the heat transport anomaly replaces ‘‘missing’’ radiative forcing over land by moving heat from ocean to land, warming the land surface. The heat transport anomaly remains substantial in steady state. These results are consistent with earlier studies that found that both land and ocean surface temperature changes may be approximated as local responses to global mean radiative forcing. The modeled heat transport anomaly has large impacts on surface heat fluxes but small impacts on precipitation, circulation, and cloud radiative forcing compared with the impacts of surface temperature change. No substantial nonlinearities are found in these atmospheric variables when the effects of forcing and surface temperature change are added.