Thermo-responsive microphase separated supramolecular polyurethanes

The ability to generate very stable assemblies via non-covalent interactions has enabled materials to be constructed that were not feasible via traditional covalent bond formation processes. A series of low molecular mass bisurethane and bisurea polymers have been developed that form stable self-assembled networks through hydrogen bonding interactions. Thermo-responsive polymers were generated by end-capping poly(ethylene-co-butylene) or polybutadiene chains with the bisurethane or bisurea motif. Microphase separation is observed via TEM and small-angle X-ray scattering (SAXS) for the modified pseudo polymers and significant differences in the temperature dependence of microphase separation are analysed via SAXS. The importance of the polarity of the end groups is manifested in distinct temperature-dependent microphase separation behaviour. Information on the local hydrogen bonding structure is provided by wide-angle X-ray scattering and variable temperature FTI

Apolipoprotein E enrichment of immuno-separated chylomicron and chylomicron remnants following saturated fatty acids

Aim: We examined the effect of meat fatty acids on lipid and apolipoprotein concentrations of very low density lipoprotein (VLDL) and chylomicron/chylomicron remnants in lipid fractions with a Svedberg flotation rate (S-f) 60-400 and S-f 20-60. Methods and results: Six healthy middle-aged men received in random order mixed meals enriched with saturated (SFA), polyunsaturated (PUFA) or monounsaturated (MUFA) fatty acids on 3 occasions. VLDL and chylomicron/chylomicron remnants in the lipid fractions were separated by immunoaffinity chromatography against apo B-100. In the S-f 60-400 chylomicron/chylomicron remnants, triacylglycerol and cholesterol concentrations were significantly tower following PUFA compared with SFA and MUFA (P <= 0.05). Apolipoprotein (apo) E responses were significantly higher after SFA in chylomicron/chylomicron remnants and VLDL compared with PUFA and MUFA (P < 0.007). However, apo B responses (particle number) were higher following MUFA than SFA (P = 0.039 for chylomicron/chylomicron remnants). Composition of the chylomicron/chylomicron remnants (expressed per particle) revealed differences in their triacylglycerol and apo E contents; in the Sf 60-400 fraction, SFA-rich chylomicron/chylomicron remnants contained significantly more triacylglycerol than MUFA (P = 0.028), more apo E than PUFA- and MUFA-rich particles (P < 0.05) and in the S-f 20-60 fraction, more apo E than MUFA (P = 0.009). Conclusion: There are specific differences in the composition of chylomicron/ chylomicron remnants formed after saturated compared with unsaturated fatty acid-rich meals which could determine their metabolic fate in the circulation and subsequent atherogenicity. (C) 2005 Elsevier B.V. All rights reserved.

Phase separated structures in tethered dPS–PMMA copolymer films revealed using X-ray scattering with a novel contrast enhancement agent

Tethered deuterated polystyrene-block-polymethyl methacrylate films have been examined by X-ray scattering both in their native state and following treatment with ruthenium tetroxide. The use of the stain, while increasing the thickness of the films, does not significantly alter the lateral structure or periodicity of the films and provides contrast between the two blocks. Both the periodicity of the films and the structure normal to the surface have been identified following staining. Experiments were also performed on films treated by a solvent exchange process, and the effects of staining on these films are discussed.

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.

Natural caprine whey oligosaccharides separated by membrane technology and profile evaluation by capillary electrophoresis

The functional food market is growing rapidly and membrane processing offers several advantages over conventional methods for separation, fractionation and recovery of bioactive components. The aim of the present study was to select a process that could be implemented easily on an industrial scale for the isolation of natural lactose-derived oligosaccharides (OS) from caprine whey, enabling the development of functional foods for clinical and infant nutrition. The most efficient process was the combination of a pre-treatment to eliminate proteins and fat, using an ultrafiltration (UF) membrane of 25 kDa molecular weight cut off (MWCO), followed by a tighter UF membrane with 1 kDa MWCO. Circa 90% of the carbohydrates recovered in the final retentate were OS. Capillary electrophoresis was used to evaluate the OS profile in this retentate. The combined membrane-processing system is thus a promising technique for obtaining natural concentrated OS from whey. Powered

Ac and dc magnetotransport properties of the phase-separated La(0.6)Y(0.1)Ca(0.3)MnO(3) manganite

The physical properties of the La(0.6)Y(0.1)Ca(0.3)MnO(3) compound have been investigated, focusing on the magnetoresistance phenomenon studied by both dc and ac electrical transport measurements. X-ray diffraction and scanning electron microscopy analysis of ceramic samples prepared by the sol-gel method revealed that specimens are single phase and have average grain size of similar to 0.5 mu m. Magnetization and 4-probe dc electrical resistivity rho(T,H) experiments showed that a ferromagnetic transition at T(C) similar to 170 K is closely related to a metal-insulator (MI) transition occurring at essentially the same temperature T(MI). The magnetoresistance effect was found to be more pronounced at low applied fields (H <= 2.5 T) and temperatures close to the MI transition. The ac electrical transport was investigated by impedance spectroscopy Z(f,T,H) under applied magnetic field H up to 1 T. The Z(f,T,H) data exhibited two well-defined relaxation processes that exhibit different behaviors depending on the temperature and applied magnetic field. Pronounced effects were observed close to T (C) and were associated with the coexistence of clusters with different electronic and magnetic properties. In addition, the appreciable decrease of the electrical permittivity epsilon`(T,H) is consistent with changes in the concentration of e(g) mobile holes, a feature much more pronounced close to T (C).

Synthesis and structure of new oligomethylene-bridged double ladders. How far can the layers be separated?

The synthesis of the α,ω-bis[dichloro(trimethylsilylmethyl)stannyl]alkanes, (Me₃SiCH₂)C1₂Sn(CH₂)_nSnCl₂(CH₂SiMe₃) (13, n=5; 14, n=6; 15, n=7; 16, n=8; 17, n=10; 18, n=12) and the corresponding oligomethylene-bridged diorganotin oxides [(Me₃SiCH₂)(O)Sn(CH₂)_nSn(O)(CH₂SiMe₃)]_m (19, n=5; 20, n=6; 21, n=7; 22, n=8; 23, n=10; 24; n=12) is reported. The reaction of the diorganodichlorostannanes 13–18 with the corresponding diorganotin oxides 19–24 provided the spacer-bridged tetraorganodistannoxanes {[(Me₃SiCH₂)ClSn(CH₂)_nSnCl(CH₂SiMe₃)]O}₄ (25, n=5; 26, n=6; 27, n=7; 28, n=8; 29, n=10; 30, n=12). Compounds 13–30 have been identified by elemental analyses and multinuclear NMR spectroscopy. Compounds 25, 27, 29 and 30 have also been characterised by single crystal X-ray diffraction analysis and electrospray mass spectrometry. For the latter the essential double ladder motif is maintained for all n in the solid state, but subtle changes in alignment of the ladder planes occur. Separation between the two layers of the double ladder ranges from approx. 8.7  Å (for 25, n=5) to approx. 15 Å (for 30, n=12). In solution there is some dissociation of the double ladders into the corresponding dimers. The degree of dissociation is favoured by increasing oligomethylene chain length n.

Efficient and accurate set-based registration of time-separated aerial images

This paper addresses the task of time-separated aerial image registration. The ability to solve this problem accurately and reliably is important for a variety of subsequent image understanding applications. The principal challenge lies in the extent and nature of transient appearance variation that a land area can undergo, such as that caused by the change under illumination conditions, seasonal variations, or the occlusion by non-persistent objects (people, cars). Our work introduces several major novelties (i) unlike previous work on aerial image registration, we approach the problem using a set-based paradigm; (ii) we show how image space local, pair-wise constraints can be used to enforce a globally good registration using a constraints graph structure; (iii) we show how a simple holistic representation derived from raw aerial images can be used as a basic building block of the constraints graph in a manner which achieves both high registration accuracy and speed; (iv) lastly, we introduce a new and, to the best of our knowledge, the only data corpus suitable for the evaluation of set-based aerial image registration algorithms. Using this data set, we demonstrate (i) that the proposed method outperforms the state-of-the-art for pair-wise registration already, achieving greater accuracy and reliability, while at the same time reducing the computational cost of the task and (ii) that the increase in the number of available images in a set consistently reduces the average registration error, with a major difference already for a single additional image.

Functional replacement across species pools of vertebrate scavengers separated at a continental scale maintains an ecosystem function

Summary: The composition of species pools can vary in space and time. While many studies are focused on understanding which factors influence the make-up of species pools, the question to which degree biogeographic variation in species composition propagates to biogeographic variation in ecological function is rarely examined. If different local species assemblages operate in ways that maintain specific ecological processes across continents, they can be regarded as functionally equivalent. Alternatively, variation in species assemblages might result in the loss of ecological function if different species fulfil different functions, and thereby fail to maintain the ecological process. Here, we test whether ecological function is affected by differences in the composition of species pools across a continental scale, comparing a tropical with a temperate pool. The model systems are assemblages of vertebrates foraging on ocean beaches, and the ecological function of interest is the consumption of wave-cast carrion, a pivotal process in sandy shore ecosystems. We placed fish carcasses (n = 179) at the beach-dune interface, monitored by motion-triggered cameras to record scavengers and quantify the detection and removal of carrion. Scavenging function was measured on sandy beaches in two distinct biogeographic regions of Australia: tropical north Queensland and temperate Victoria. The composition of scavenging assemblages on sandy beaches varied significantly across the study domain. Raptors dominated in the tropics, while invasive red foxes were prominent in temperate assemblages. Notwithstanding the significant biogeographic change in species composition, ecological function - as indexed by carcass detection and removal - was maintained, suggesting strong functional replacement at the continental scale. Species pools of vertebrate scavengers that are assembled from taxonomically distinct groups (birds vs. mammals) and located in distinct climatic regions (temperate vs. tropical) can maintain an ecological process via replacement of species with comparable functional traits.

‘It should be a big responsibility’: Separated low-income mothers’ evaluation of child support arrangements and the conduct of fathers

The Australian Child Support Scheme was established as a means of ensuring adequate financial support for children of separated parents. However, within the financial transfer of child support exist notions of ‘trust’ and ‘fairness’ based on parents navigating their changed relationship post-separation. Previous research has explored the assessment and outcomes of child support for both payee and payer parents, however little attention has been given to how women evaluate the assessment and outcomes of child support. As such, this research aimed to explore payee mothers’ evaluation of their child support experiences based on the value of their child support assessment and the extent to which these payments were received. Following the methods of constructivist grounded theory, in-depth interviews were conducted with 20 low-income single mothers. Analysis revealed that payee mothers evaluated child support based on the moral assumptions and the rationalities they perceived were underlying payer fathers’ child support compliance. While payee mothers desired arrangements that reflected joint parental financial responsibility, in reality many experienced problematic child support payments, which may ultimately undermine payee parents’ confidence in the Child Support Scheme.

Spider assemblages in widely-separated patches of cerrado in São Paulo State, Brazil.

Brazilian cerrado is a biologically-rich, poorly understood, yet rapidly disappearing habitat. Composition of the spider assemblages from areas of cerrado from three separate sites in the State of São Paulo, Brazil were sampled by beating the canopies and adjacent shrubs of three Myrcia (Myrtaceae; "myrtle") tree species. These produced a total of 859 spiders 'belonging to 21 families and 75 species. The most undisturbed and densest cerrado habitat had the largest number and greatest diversity of spider species, encompassing stalkers, ambushers, space web-weavers, and foliage runners. The other two areas were dominated by foliage runners. Spider distribution in this natural and complex habitat was evaluated by classifying the samples into 12 habitat/microhabitat groups according to local of the patch, tree species, and microhabitat (target tree or adjacent shrub). Correspondence analysis was used for ordination of species and groups based on their abundance. Environmental factors such as patches type (p=0.027) and plant species (p=0.046) had significant effects in explaining the ordination. Canonical correspondence analysis was applied for relating the patterns in species richness and/or abundance to the significant environmental factors. A comparison of the results showed that the family composition among the patches is rather similar, and there is a tendency of spiders species overlap an interregional level (patches effect, p=0.027). However, the most similar spider assemblages living on woody vegetation occurred in Myrcia venulosa and Myrcia guianensis at São Carlos and Pirassununga, demonstrating an interregional similarity (plant species effect, p=0.046) that indicates an association between spiders and particular vegetation.