A molecular T-matrix approach to calculating low-energy electron diffusion intensities for ordered molecular adsorbates

We present a novel approach to calculating Low-Energy Electron Diffraction (LEED) intensities for ordered molecular adsorbates. First, the intra-molecular multiple scattering is computed to obtain a non-diagonal molecular T-matrix. This is then used to represent the entire molecule as a single scattering object in a conventional LEED calculation, where the Layer Doubling technique is applied to assemble the different layers, including the molecular ones. A detailed comparison with conventional layer-type LEED calculations is provided to ascertain the accuracy of this scheme of calculation. Advantages of this scheme for problems involving ordered arrays of molecules adsorbed on surfaces are discussed.

Finite- N effects for ideal polymer chains near a flat impenetrable wall

This paper addresses the statistical mechanics of ideal polymer chains next to a hard wall. The principal quantity of interest, from which all monomer densities can be calculated, is the partition function, G N(z) , for a chain of N discrete monomers with one end fixed a distance z from the wall. It is well accepted that in the limit of infinite N , G N(z) satisfies the diffusion equation with the Dirichlet boundary condition, G N(0) = 0 , unless the wall possesses a sufficient attraction, in which case the Robin boundary condition, G N(0) = - x G N ′(0) , applies with a positive coefficient, x . Here we investigate the leading N -1/2 correction, D G N(z) . Prior to the adsorption threshold, D G N(z) is found to involve two distinct parts: a Gaussian correction (for z <~Unknown control sequence '\lesssim' aN 1/2 with a model-dependent amplitude, A , and a proximal-layer correction (for z <~Unknown control sequence '\lesssim' a described by a model-dependent function, B(z).

Double-gyroid morphology of a polystyrene-block-poly(ferrocenylethylmethylsilane) diblock copolymer: a route to ordered bicontinuous nanoscale architectures

A polystyrene-block-poly(ferrocenylethylmethylsilane) diblock copolymer, displaying a double-gyroid morphology when self-assembled in the solid state, has been prepared with a PFEMS volume fraction phi(PFMS)=0.39 and a total molecular weight of 64 000 Da by sequential living anionic polymerisation. A block copolymer with a metal-containing block with iron and silicon in the main chain was selected due to its plasma etch resistance compared to the organic block. Self-assembly of the diblock copolymer in the bulk showed a stable, double-gyroid morphology as characterised by TEM. SAXS confirmed that the structure belonged to the Ia3d space group.

Use of a reduced Schiff-Base ligand to prepare novel chloro-bridged chains of rare Cu(II) trinuclear complexes with mixed azido/oxo and chloro/oxo bridges

Two mixed bridged one-dimensional (1D) polynuclear complexes, [Cu3L2(mu(1,1)-N-3)(2)(mu-Cl)Cl](n) (1) and {[Cu3L2(mu-Cl)(3)Cl]center dot 0.46CH(3)OH}(n), (2), have been synthesized using the tridentate reduced Schiff-base ligand HL (2-[(2-dimethylamino-ethylamino)-methyl]-phenol). The complexes have been characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. In both complexes the basic trinuclear angular units are joined together by weak chloro bridges to form a 1D chain. The trinuclear structure of 1 is composed of two terminal square planar [Cu(L)(mu(1,1)-N-3)] units connected by a central Cu(II) atom through bridging nitrogen atoms of end-on azido ligands and the phenoxo oxygen atom of the tridentate ligand. These four coordinating atoms along with a chloride ion form a distorted trigonal bipyramidal geometry around the central Cu(II). The structure of 2 is similar; the only difference being a Cl bridge replacing the mu(1,1)-N-3 bridge in the trinuclear unit. The magnetic properties of both trinuclear complexes can be very well reproduced with a simple linear symmetrical trimer model (H = JS(i)S(i+1)) with only one intracluster exchange coupling (J) including a weak intertrimer interaction (.j) reproduced with the molecular field approximation. This model provides very satisfactory fits for both complexes in the whole temperature range with the following parameters: g = 2.136(3), J = 93.9(3) cm(-1) and zj= -0.90(3) cm(-1) (z = 2) for 1 and g = 2.073(7), J = -44.9(4) cm(-1) and zJ = -1.26(6) cm(-1) (z = 2) for 2.

How different are GM food accepters and rejecters really? A means-end chains application to yogurt in Germany

The purpose of the paper is to identify and describe differences in cognitive structures between consumer segments with differing levels of acceptance of genetically modified (GM) food. Among a sample of 60 mothers three segments are distinguished with respect to purchase intentions for GM yogurt: non-buyers, maybe-buyers and likely-buyers. A homogeneity test for the elicited laddering data suggests merging maybe- and likely-buyers, yielding two segments termed accepters and rejecters. Still, overlap between the segments’ cognitive structures is considerable, in particular with respect to a health focus in the evaluation of perceived consequences and ambivalence in technology assessment. Distinct differences are found in the assessment of benefits offered by GM food and the importance of values driving product evaluation and thus purchase decisions.

Highly proton-ordered water structures on oxygen precovered Ru{0001}

We present helium scattering measurements of a water ad-layer grown on a O(2 1)/Ru(0001) surface. The adsorbed water layer results in a well ordered helium diffraction pattern with systematic extinctions of diffraction spots due to glide line symmetries. The data reflects a well-defined surface structure that maintains proton order even at surprisingly high temperatures of 140 K. The diffraction data we measure is consistent with a structure recently derived from STM measurements performed at 6 K. Comparison with recent DFT calculation is in partial agreement, suggesting that these calculations might be underestimating the contribution of relative water molecule orientations to the binding energy.

Structure variation and evolution in microphase-separated grafted diblock copolymer films

The phase behavior of grafted d-polystyrene-block-poly(methyl methacrylate) diblock copolymer films is examined, with particular focus on the effect of solvent and annealing time. It was observed that the films undergo a two-step transformation from an initially disordered state, through an ordered metastable state, to the final equilibrium configuration. It was also found that altering the solvent used to wash the films, or complete removal of the solvent prior to thermal annealing using supercritical CO2, could influence the structure of the films in the metastable state, though the final equilibrium state was unaffected. To aid in the understanding to these experimental results, a series of self-consistent field theory calculations were done on a model diblock copolymer brush containing solvent. Of the different models examined, those which contained a solvent selective for the grafted polymer block most accurately matched the observed experimental behavior. We hypothesize that the structure of the films in the metastable state results from solvent enrichment of the film near the film/substrate interface in the case of films washed with solvent or faster relaxation of the nongrafted block for supercritical CO2 treated (solvent free) films. The persistence of the metastable structures was attributed to the slow reorganization of the polymer chains in the absence of solvent.

Crystallization of random aromatic copolyesters containing flexible spacer chains and side-groups

The crystallization behaviour of a series of random copolymers of varying chemical composition is reported. For polymers containing a high proportion of alternating rigid aromatic units and flexible spacers, conventional liquid crystalline and crystalline phase behaviour is observed. The introduction of a substantial fraction of a second shorter rigid unit containing side-chains leads to a broad endotherm in the d.s.c. scan covering some 150°C. Subsequent isothermal crystallization at any point within the broad endotherm leads to the generation of sharp endotherms at temperatures just above the recrystallization temperature. We attribute this behaviour to the crystallization of clusters of molecules containing similar random sequences. Such crystals are non-periodic along the chain direction.

Evaluating the likelihood of the adoption of an animal welfare assessment system in European agri-food supply chains

Purpose – The purpose of this paper is to analyse the likelihood of adoption of a recently designed Welfare Assessment System in agri-food supply chains and the factors affecting the adoption decision. The application is carried out for pig and poultry chains. Design/methodology/approach – This research consisted of two main components: interviews with retailers in pig and poultry supply chains in eight different EU countries to explore their perceptions towards the adoption possibilities of the welfare assessment system; and a conjoint analysis designed to evaluate the perceived adoption likelihood of the assessment system by different Standards Formulating Organisations (SFOs). Findings – Stakeholders were found to be especially concerned about the costs of implementation of the system and how it could, or should, be merged with existing assurance schemes. Another conclusion of the study is that the presence of a strong third independent party supporting the implementation of the welfare assessment system would be the most important influence on the decision whether, or not, to adopt it. Originality/value – This research evaluates the adoption possibilities of a novel Welfare Assessment System and presents the views of different supply chain stakeholders on an adoption of such a system. The main factors affecting the adoption decision are identified and analysed. Contrary to expectations, the costs of adoption of a new welfare assessment system were not considered to be the most important factor affecting the decision of supply chain stakeholders about the adoption of this new welfare system.

Control of strand registry by attachment of PEG chains to amyloid peptides influences nanostructure

The self-assembly in aqueous solution of PEG-peptide conjugates comprising a model amyloid peptide sequence FFKLVFF that contains the Ab(16–20) KLVFF motif is investigated. X-ray diffraction reveals different packing motifs dependent on PEG chain length. This is correlated to remarkable differences in self-assembled nanostructures. The control of strand registry points to a subtle interplay between aromatic stacking, electrostatic and amphiphilic interactions.