Infrared linear dichroism spectroscopy on amyloid fibrils aligned by molecular combing

We report the use of molecular combing as an alignment method to obtain macroscopically oriented amyloid fibrils on planar surfaces. The aligned fibrils are studied by polarized infrared spectroscopy. This gives structural information that cannot be definitively obtained from standard infrared experiments on isotropic samples, for example, confirmation of the characteristic cross-beta amyloid core structure, the side-chain orientation from specific amino acids, and the arrangement of the strands within the fibrils, as we demonstrate here. We employed amyloid fibrils from hen egg white lysozyme (HEWL) and from a model octapeptide. Our results demonstrate molecular combing as a straightforward method to align amyloid fibrils, producing highly anisotropic infrared linear dichroism (IRLD) spectra.

Time-dependent orientation coupling in equilibrium polymer melts

The motion in concentrated polymer systems is described by either the Rouse or the reptation model, which both assume that the relaxation of each polymer chain is independent of the surrounding chains. This, however, is in contradiction with several experiments. In this Letter, we propose a universal description of orientation coupling in polymer melts in terms of the time-dependent coupling parameter κ(t). We use molecular dynamics simulations to show that the coupling parameter increases with time, reaching about 50% at long times, independently of the chain length or blend composition. This leads to predictions of component dynamics in mixtures of different molecular weights from the knowledge of monodisperse dynamics for unentangled melts. Finally, we demonstrate that entanglements do not play a significant role in the observed coupling. © 2010 The American Physical Society

Coupling between mesogenic units and polymer backbone in side-chain liquid crystal polymers and elastomers

The levels of alignment of the mesogenic units and of the polymer backbone trajectory for polyacrylate based nematic side-chain liquid crystal polymers and elastomers were evaluated by using wide angle X-ray and small angle neutron scattering procedures. The X-ray scattering measurements show that substantial levels of preferred orientation of the mesogenic units may be introduced through magnetic fields for uncrosslinked polymers and through mechanical extension for liquid crystal elastomers. Small angle neutron scattering measurements show that for highly aligned samples an anisotropic polymer backbone trajectory is observed in which the envelope is slightly extended by ∼ 10% in the direction parallel to the axis of alignment of the mesogenic units. The sense of this coupling differs from that recorded for other uncrosslinked side-chain liquid crystal polymers. Possible mechanisms to account for this anisotropy and its relationship to the properties of liquid crystal elastomers are discussed. The observed deformation behaviour of the liquid crystal elastomer is non-affine and this appears to confirm the dominating influence of the liquid crystal order of the side chains on the mechanical properties of these novel networks.

Adsorption, orientation and thermal decomposition of copper(II) hexafluoroacetylacetonate on rutile TiO2(110)

We have investigated the adsorption and thermal decomposition of copper hexafluoroacetylacetonate (Cu-11(hfaC)(2)) on single crystal rutile TiO2(110). Low energy electron diffraction shows that room temperature saturation coverage of the Cu-II(hfac)(2) adsorbate forms an ordered (2 x 1) over-layer. X-ray and ultra-violet photoemission spectroscopy of the saturated surface were recorded as the sample was annealed in a sequential manner to reveal decomposition pathways. The results show that the molecule dissociatively adsorbs by detachment of one of the two ligands to form hfac and Cu-1(hfac) which chemisorb to the substrate at 298 K. These ligands only begin to decompose once the surface temperature exceeds 473 K where Cu core level shifts indicate metallisation. This reduction from Cu(I) to Cu(0) takes place in the absence of an external reducing agent and without disproportionation and is accompanied by the onset of decomposition of the hfac ligands. Finally, C K-edge near edge X-ray absorption fine structure experiments indicate that both the ligands adsorb aligned in the < 001 > direction and we propose a model in which the hfac ligands adsorb on the 5-fold coordinated Ti atoms and the Cu-1(hfac) moiety attaches to the bridging O atoms in a square planar geometry. The calculated tilt angle for these combined geometries is approximately 10 degrees to the surface normal.

Synthesis and characterization of thermally stable second-order nonlinear optical side-chain polyimides containing thiazole and benzothiazole push-pull chromophores

Push-pull nonlinear optical (NLO) chromophores containing thiazole and benzothiazole acceptors were synthesized and characterized. Using these chromophores a series of second-order NLO polyimides were Successfully prepared from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), pyromellitic dianhydride (PMDA) and 3,3'4,4'-benzophenone tetracarboxylic dianhydride (BTDA) by a standard condensation polymerization technique. These polyimides exhibit high glass transition temperatures ranging from 160 to 188 degrees C. UV-vis spectrum of polyimide exhibited a slight blue shift and decreases in absorption due to birefringence. From the order parameters, it was found that chromophores were aligned effectively. Using in situ poling and temperature ramping technique, the optical temperatures for corona poling were obtained. It was found that the optimal temperatures of polyimides approach their glass transition temperatures. These polyimides demonstrate relatively large d(33) values range between 35.15 and 45.20 pm/V at 532 nm. (C) 2008 Elsevier B.V. All rights reserved.

Food-chain transfer of zinc from contaminated Urtica dioica and Acer pseudoplatanus L. to Microlophium carnosum and Drepanosiphum platanoidis Schrank

This study examines the food-chain transfer of Zn from two plant species, Urtica dioica (stinging nettle) and Acer pseudoplatanus (sycamore maple), into their corresponding aphid species, Microlophium carnosum and Drepanosiphum platanoidis. The plants were grown in a hydroponic system using solutions with increasing concentrations of Zn from 0.02 to 41.9 mg Zn/l. Above-ground tissue concentrations in U. dioica and M. carnosum increased with increasing Zn exposure (p < 0.001). Zn concentrations in A. pseudoplatanus also increased with solution concentration from the control to the 9.8 mg Zn/l solution, above which concentrations remained constant. Zn concentrations in both D. platanoidis and the phloem tissue of A. pseudoplatanus were not affected by the Zn concentration in the watering solution. It appears that A. pseudoplatanus was able to limit Zn transport in the phloem, resulting in constant Zn exposure to the aphids. Zn concentrations in D. platanoidis were around three times those in M. carnosum. Concentrations of Zn in two aphid species are dependant on species and exposure.

Voices from the aid 'chain': The personal dynamics of care

This paper uses a simplified model of the aid 'chain' to explore some causes and consequences of breakdown in communication. Although the rhetoric of Northern-based donors is awash with words such as 'partnership' and 'inclusion' when dealing with their Southern-based partners, the situation in practice is different. Unequal power relationships sometimes result in donor imposition of Perspectives and values. It is our contention, based on a collective experience of fifty-four years in a Nigerian-based non-governmental development organization (NGDO), the Diocesan Development Services (DDS), that much of the driving force behind the successes and problems faced by the institution was founded on relationships that evolved between individuals. In order to understand why things happened the way they did it is necessary to begin with the human element that cannot be condensed into objects or categories. While injudicious donor interference bad damaging repercussions, our experience suggests that care and consideration flow throughout the aid chain and actions are not malevolent. Breakdowns can be attributed to a number of factors, with the over-riding one being pressures operating at the personal level that emanate from within the institution itself and the larger community. The paper analyses three experiences using institutional ethnography theory and methodologies as a basis. Examples taken address the influence key donor personnel had in the function of DDS, and how these changed with time. The mission, policies and even procedures of the donor did not change markedly over thirty-two years, but each changing desk officer had their own philosophy and approach and a different interpretation of their own institutional policies. Hence while the 'macro' has an influence it is mediated via individual interpretation. In our view, the importance of people-people relationships is particularly understated in development literature where emphasis gravitates towards the aggregate and global.

Creating a greater partnership: analysing partnership in the Catholic Church development chain

This paper presents results from a project designed to explore the meaning and function of partnership within the Catholic Church development chain. The geography literature has had little to say about such aid chains, especially those founded on faith-based groups. The relationships between three Catholic Church-based donors - referred to as A, B and C - with development personnel of the diocese of the Abuja Ecclesiastical Province (AEP) as well as other Catholic Church structures in Nigeria were analysed. The aim was to explore the forces behind the relationships and how 'patchy' these relationships were in AEP. Respondents were asked to give each of the donors a score in relation to four questions covering their relationship with the donors. Results suggest that the modus operandi of donor 'A' allows it to be perceived as the 'best' partner, while 'B' was scored less favourably because of a perception that it attempts to act independently of existing structures in Nigeria rather than work through them. There was significant variation between diocese in this regard, as well as between the diocese and other structures of the Church (Provinces, Inter-Provinces and National Secretariat). Thus 'partnership' in the Catholic Church aid chain is a highly complex, contested and 'visioned' term and the development of an analytical framework has to take account of these fundamentals.

Food-chain transfer of cadmium and zinc from contaminated Urtica dioica to Helix aspersa and Lumbricus terrestris

The present study examines the potential of Urtica dioica as an ecologically relevant species for use in ecotoxicological testing. It is prevalent in degraded ecosystems and is a food source for invertebrates. Urtica dioica grown in hydroponic solutions containing from less than 0.003 to 5.7 mg Cd/L or from 0.02 to 41.9 mg Zn/L accumulated metals resulting in leaf tissue concentrations in the range of 0.10 to 24.9 mg Cd/kg or 22.5 to 2,772.0 mg Zn/kg. No toxicological effects were apparent except at the highest concentrations tested, suggesting that this species may be an important pathway for transfer of metals to primary plant consumers. Helix aspersa and Lumbricus terrestris were fed the Cd- and Zn-rich leaves of U. dioica for six and four weeks, respectively. Cadmium and Zn body load increased with increasing metal concentration in the leaves (p < 0.001). Ratios of invertebrate metal concentration to leaf metal concentration were in the range of 1:0.03 to 1:1.4 for Cd and 1:0.2 to 1:2.8 for Zn in H. aspersa and 1:0.002 to 1:3.9 for Cd and 1:0.2 to 1:8.8 for Zn in L. terrestris. Helix aspersa Cd and Zn tissue concentrations (15.5 and 1,220.2 mg/kg, respectively) were approximately threefold those in L. terrestris when both species were fed nettle leaves with concentrations of approximately 23 mg Cd/ kg and 3,400 mg Zn/kg. Models demonstrate that L. terrestris Cd tissue concentrations (r(2) = 0.74, p < 0.001) and H. aspersa Zn tissue concentrations (r(2) = 0.69, p < 0.001) can be estimated from concentrations of Cd and Zn within the leaves of U. dioica and suggest that reasonably reproducible results can be obtained using these species for ecotoxicological testing.

Financial protection in the UK building industry: a guide for clients and the construction supply chain.

There is a clear need for financial protection in the construction industry, both to guarantee satisfactory completion of construction projects and to guard against non-payment. However, the cost of financial protection is often felt to be disproportionately high, with unnecessary overlap between different measures. The Reading Construction Forum has commissioned and steered research which is published in this report in an effort to bring the problem out into the open and to clarify the various options open to the various parties and stakeholders in the construction process. "Financial Protection in the UK Building Industry" is the first definitive report on the subject, offering an accurate and simple guide that all levels within the construction industry can understand. This accessible new guide considers the problem of financial protection and clearly lays out the alternative solutions.It looks by turn at the client, the main contractor, and the sub-contractor, discussing which financial protection options are available to each of them, and considers the pros and cons of each option. The cost of each type of financial protection is weighed against the amount of protection provided and the risks involved. The book concludes with guidance for consultants, emphasising relevant points to consider when advising clients and contractors about which type of financial protection to choose. "Financial Protection in the UK Building Industry" was researched by a literature search, collection of statistical data, and financial data, as well as discussions with clients, contractors, sub-contractors and consultants. This investigation has shown that the direct costs of implementing financial protection measures are marginal, and that wider adoption of payment protection would create a more equitable situation between contracting parties.This guide will enable anyone in the construction industry to consider all the options, and determine what is the best solution for them. "Reading Construction Forum Financial Protection for the UK Building Industry" was complied by the University of Reading, funded by the Reading Construction Forum. The Forum has recently commissioned and steered a number of high-profile reports covering important aspects of the construction industry. Members of the Forum include major companies which are concerned with achieving high quality in the design, construction and use of commercial, retail and industrial buildings. All are committed to change and innovation in the British and European construction industries.

Effect of acyl chain length on transfection efficiency and toxicity of polyethylenimine

Polyethylenimine (PEI) is an efficient nonviral gene delivery vector because of its high buffering capacity and DNA condensation ability. In our study, the amino groups on the polymeric backbone were acylated using acetic or propionic anhydride to alter the protonation behaviour and the hydrophilic/hydrophobic balance of the polymer. The concentration of acylated primary amines was determined using trinitrobenzene sulphonic acid assay. Results showed that our modified polymers had lower buffering capacities in solutions compared to PEI. The polymers were complexed with plasmid encoding enhanced green fluorescent protein at three different ratios (1:1, 1:2 and 1:10 w/w DNA to polymer) to form polyplexes and their toxicities and transfection efficiencies were evaluated in HEK 293 cells. Acylation reduced the number of primary amines on the polymer and the surface charge, improving haemocompatibility and reducing cytotoxicity. The reduction in the concentration of amino groups helped to optimise DNA compaction and facilitated polyplex dissociation in the cell, which increased transfection efficiency of the modified polymers compared to the parent polymer. Polymers with buffering capacities greater than 50% and less than 80% relative to PEI, showed higher transfection efficiencies than PEI. The propionic anhydride modified polymers had appropriate interactions with DNA which provided both DNA compaction and polyplex dissociation. These systems interacted better with the cell membrane because of their slightly higher lipophilicity and formed polyplexes which were less cytotoxic than polyplexes of acetic anhydride modified polymers. Among the vectors tested, 1:0.3 mol/mol PEI:propionic anhydride in a 1:2 w/w DNA:polymer composition provided the best transfection system with improved transfection efficiency and reduced cytotoxicity.