Hyperbranched polydendrons: a new controlled macromolecular architecture with self-assembly in water and organic solvents

A new macromolecular architecture (hyperbranched polydendrons) is presented. Combining aspects of linear-dendritic hybrids, controlled radical polymerisation and branched vinyl polymerisation, the materials have very high molecular weight (Mw > 1 MDa) and surface functionality. Although dispersities are broad (Đ up to 25) the structures behave with remarkable uniformity upon manipulation of solvent environment. Comparisons of conventional linear-dendritic hybrids and hyperbranched polydendrons are presented, including aspects of their synthesis. Under solvent exchange in organic media, a reversible self-assembly to form monodispersed nanoparticles (PDI as low as 0.013) is observed. Self-assembly and encapsulation is also observed during aqueous nanoprecipitation of the hyperbranched materials, with nanoparticle size (diameters from 60–140 nm) controlled through modification of precipitation conditions and the generation of the ideally branched dendrons at one end of each primary chain. The aqueous nanoparticles are highly stable and offer considerable opportunities for tailored functionality and future advanced applications.</div

One slope or two? Detecting statistically significant breaks of slope in geophysical data, with application to fracture scaling relationships

The scaling of displacement as a function of length is important for a variety of applications which depend on the mechanical and hydraulic properties of faults and fractures. Recently it has been suggested that the power-law exponent nu which has been found to characterise this relationship may change significantly at a characteristic length for a variety of reasons, for example when cracks begin to interact, or when faults grow to a length comparable to a characteristic size in the brittle layer. Such a break of slope requires a second straight line, requiring two extra model parameters. Here we present a new method for analysing such data, which penalises the extra parameters using a modified form of Schwarz's Information Criterion, and a Bayesian approach which represents uncertainty in the unknown parameters. We apply the method to data from the Krafla fissure zone in the north of Iceland, and find a significant break of slope, from nu approximate to 3/2 to nu approximate to 2/3, at a characteristic length of 12 m

In Situ Small-Angle X-ray Scattering Studies During Reversible Addition–Fragmentation Chain Transfer Aqueous Emulsion Polymerization

Polymerization-induced self-assembly (PISA) is a powerful platform technology for the rational and efficient synthesis of a wide range of block copolymer nano-objects (e.g., spheres, worms or vesicles) in various media. In situ small-angle X-ray scattering (SAXS) studies of reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization have previously provided detailed structural information during self-assembly (see M. J. Derry et al., Chem. Sci. 2016, 7, 5078–5090). However, conducting the analogous in situ SAXS studies during RAFT aqueous emulsion polymerizations poses a formidable technical challenge because the inherently heterogeneous nature of such PISA formulations requires efficient stirring to generate sufficiently small monomer droplets. In the present study, the RAFT aqueous emulsion polymerization of 2-methoxyethyl methacrylate (MOEMA) has been explored for the first time. Chain extension of a relatively short non-ionic poly(glycerol monomethacrylate) (PGMA) precursor block leads to the formation of sterically-stabilized PGMA-PMOEMA spheres, worms or vesicles, depending on the precise reaction conditions. Construction of a suitable phase diagram enables each of these three morphologies to be reproducibly targeted at copolymer concentrations ranging from 10 to 30% w/w solids. High MOEMA conversions are achieved within 2 h at 70 °C, which makes this new PISA formulation well-suited for in situ SAXS studies using a new reaction cell. This bespoke cell enables efficient stirring and hence allows in situ monitoring during RAFT emulsion polymerization for the first time. For example, the onset of micellization and subsequent evolution in particle size can be studied when preparing PGMA29-PMOEMA30 spheres at 10% w/w solids. When targeting PGMA29-PMOEMA70 vesicles under the same conditions, both the micellar nucleation event and the subsequent evolution in the diblock copolymer morphology from spheres to worms to vesicles are observed. These new insights significantly enhance our understanding of the PISA mechanism during RAFT aqueous emulsion polymerization

Stature and sibship: historical evidence

This paper examines historical evidence for a quality–quantity trade-off between sibship size and height as an indicator of health. The existing literature has focused more on education than on health and it has produced mixed results. Historical evidence is limited by the lack of household-level data with which to link an individual’s height with his or her childhood circumstances. Nevertheless a few recent studies have shed light on this issue. Evidence for children in interwar Britain and for soldiers born in the 1890s who enlisted in the British army at the time of World War I is reviewed in detail. Both studies support the idea of a significant trade-off, partly due to income dilution and partly because, in these settings, large families were a conduit for infection. Evidence from country-level time series is consistent with this view. The fertility decline that began in the late nineteenth century made a modest but nevertheless significant contribution to the overall increase in heights during the following half-century

Enabling the Collaborative Definition of DSMLs

International audienceSoftware development processes are collaborative in nature. Neglecting the key role of end-users leads to software that does not satisfy their needs. This collaboration becomes specially important when creating Domain-Specific Modeling Languages (DSMLs), which are (modeling) languages specifically designed to carry out the tasks of a particular domain. While end-users are actually the experts of the domain for which a DSML is developed, their participation in the DSML specification process is still rather limited nowadays. In this paper we propose a more community-aware language development process by enabling the active participation of all community members (both developers and end-users of the DSML) from the very beginning. Our proposal is based on a DSML itself, called Collaboro, which allows representing change proposals on the DSML design and discussing (and tracing back) possible solutions, comments and decisions arisen during the collaboration

On the evolution of clustering of 24um-selected galaxies

This paper investigates the clustering properties of a complete sample of 1041 24um-selected sources brighter than F[24um]=400 uJy in the overlapping region between the SWIRE and UKIDSS UDS surveys. We have concentrated on the two (photometric) interval ranges z=[0.6-1.2] (low-z sample) and z>1.6 (high-z sample) as it is in these regions were we expect the mid-IR population to be dominated by intense dust-enshrouded activity such as star formation and black hole accretion. Investigations of the angular correlation function produce a correlation length are r0~15.9 Mpc for the high-z sample and r0~8.5 Mpc for the low-z one. Comparisons with physical models reveal that the high-z sources are exclusively associated with very massive (M>~10^{13} M_sun)haloes, comparable to those which locally host groups-to-clusters of galaxies, and are very common within such (rare) structures. Conversely, lower-z galaxies are found to reside in smaller halos (M_min~10^{12} M_sun) and to be very rare in such systems. While recent studies have determined a strong evolution of the 24um luminosity function between z~2 and z~0, they cannot provide information on the physical nature of such an evolution. Our clustering results instead indicate that this is due to the presence of different populations of objects inhabiting different structures, as active systems at z<~1.5 are found to be exclusively associated with low-mass galaxies, while very massive sources appear to have concluded their active phase before this epoch. Finally, we note that the small-scale clustering data seem to require steep profiles for the distribution of galaxies within their halos. This is suggestive of close encounters and/or mergers which could strongly favour both AGN and star-formation activity.Comment: 13 pages, 8 figures, to appear in MNRA

Directional wetting in anisotropic inverse opals

Porous materials display interesting transport phenomena due to the restricted motion of fluids within the nano- to micro-scale voids. Here, we investigate how liquid wetting in highly ordered inverse opals is affected by anisotropy in pore geometry. We compare samples with different degrees of pore asphericity and find different wetting patterns depending on the pore shape. Highly anisotropic structures are infiltrated more easily than their isotropic counterparts. Further, the wetting of anisotropic inverse opals is directional, with liquids filling from the side more easily. This effect is supported by percolation simulations as well as direct observations of wetting using time-resolved optical microscopy

Limited effect of patient and disease characteristics on compliance with hospital antimicrobial guidelines

Objective: Physicians frequently deviate from guidelines that promote prudent use of antimicrobials. We explored to what extent patient and disease characteristics were associated with compliance with guideline recommendations for three common infections. Methods: In a 1-year prospective observational study, 1,125 antimicrobial prescriptions were analysed for compliance with university hospital guidelines. Results: Compliance varied significantly between and within the groups of infections studied. Compliance was much higher for lower respiratory tract infections (LRTIs; 79%) than for sepsis (53%) and urinary tract infections (UTIs; 40%). Only predisposing illnesses and active malignancies were associated with more compliant prescribing, whereas alcohol/ intravenous drug abuse and serum creatinine levels > 130 mu mol/l were associated with less compliant prescribing. Availability of culture results had no impact on compliance with guidelines for sepsis but was associated with more compliance in UTIs and less in LRTIs. Narrowing initial broad-spectrum antimicrobial therapy to cultured pathogens was seldom practised. Most noncompliant prescribing concerned a too broad spectrum of activity when compared with guideline-recommended therapy. Conclusion: Patient characteristics had only a limited impact on compliant prescribing for a variety of reasons. Physicians seemed to practise defensive prescribing behaviour, favouring treatment success in current patients over loss of effectiveness due to resistance in future patients

A demonstration of an affinity between pyrite and organic matter in a hydrothermal setting

One of the key-principles of the iron-sulphur world theory is to bring organic molecules close enough to interact with each other, using the surface of pyrite as a substrate in a hydrothermal setting. The present paper explores the relationship of pyrite and organic matter in a hydrothermal setting from the geological record; in hydrothermal calcite veins from Carboniferous limestones in central Ireland. Here, the organic matter is accumulated as coatings around, and through, pyrite grains. Most of the pyrite grains are euhedral-subhedral crystals, ranging in size from ca 0.1-0.5 mm in diameter, and they are scattered throughout the matrix of the vein calcite. The organic matter was deposited from a hydrothermal fluid at a temperature of at least 200°C, and gives a Raman signature of disordered carbon. This study points to an example from a hydrothermal setting in the geological record, demonstrating that pyrite can have a high potential for the concentration and accumulation of organic materials