Synthesis, characterisation and Pickering emulsifier performance of poly(stearyl methacrylate)–poly(N-2-(methacryloyloxy)ethyl pyrrolidone) diblock copolymer nano-objects via RAFT dispersion polymerisation in n-dodecane

A near-monodisperse poly(stearyl methacrylate) macromolecular chain transfer agent (PSMA macro-CTA) was prepared via reversible addition–fragmentation chain transfer (RAFT) solution polymerisation in toluene. This PSMA macro-CTA was then utilised as a stabiliser block for the RAFT dispersion polymerisation of a highly polar monomer, N-2-(methacryloyloxy)ethyl pyrrolidone (NMEP), in n-dodecane at 90 °C. 1H NMR studies confirmed that the rate of NMEP polymerisation was significantly faster than that of a non-polar monomer (benzyl methacrylate, BzMA) under the same conditions. For example, when targeting a PSMA14–PNMEP100 diblock copolymer, more than 99% NMEP conversion was achieved within 30 min, whereas only 19% BzMA conversion was obtained on the same time scale for the corresponding PSMA14–PBzMA100 synthesis. The resulting PSMA–PNMEP diblock copolymer chains underwent polymerisation-induced self-assembly (PISA) during growth of the insoluble PNMEP block to form either spherical micelles, highly anisotropic worms or polydisperse vesicles, depending on the target DP of the PNMEP chains. Systematic variation of this latter parameter, along with the solids content, allowed the construction of a phase diagram which enabled pure morphologies to be reproducibly targeted. Syntheses conducted at 10% w/w solids led to the formation of kinetically-trapped spheres. A monotonic increase in particle diameter with PNMEP DP was observed for such PISA syntheses, with particle diameters of up to 462 nm being obtained for PSMA14–PNMEP960. Increasing the copolymer concentration to 15% w/w solids led to worm-like micelles, while vesicles were obtained at 27.5% w/w solids. High (≥95%) NMEP conversions were achieved in all cases and 3[thin space (1/6-em)]:[thin space (1/6-em)]1 chloroform/methanol GPC analysis indicated relatively high blocking efficiencies. However, relatively broad molecular weight distributions (Mw/Mn > 1.50) were observed when targeting PNMEP DPs greater than 150. This indicates light branching caused by the presence of a low level of dimethacrylate impurity. Finally, PSMA14–PNMEP49 spheres were evaluated as Pickering emulsifiers. Unexpectedly, it was found that either water-in-oil or oil-in-water Pickering emulsions could be obtained depending on the shear rate employed for homogenisation. Further investigation suggested that high shear rates lead to in situ inversion of the initial hydrophobic PSMA14–PNMEP49 spheres to form hydrophilic PNMEP49–PSMA14 spheres

The calibration of photographic and spectroscopic films: Reciprocity failure and thermal responses of IIaO film at liquid nitrogen temperatures

Reciprocity failure was examined for IIaO spectroscopic film. The results indicate reciprocity failure occurs at three distinct minimum points in time; 15 min, 30 min and 90 min. The results are unique because theory suggests only one minimum reciprocity failure point should occur. When incubating 70mm IIaO film for 15 and 30 min at temperatures of 30, 40, 50, and 60 C and then placing in a liquid nitrogen bath at a temperature of -190 C the film demonstrated an increase of the optical density when developed at a warm-up time of 30 min. Longer warm-up periods of 1, 2 and 3 hrs yield a decrease in optical density of the darker wedge patterns; whereas, shorter warm-up times yield an overall increase in the optical densities

The Effects of a Regular Yoga Practice on Psychophysiological Measures in College Students

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A prototype system for observing the Atlantic Meridional Overturning Circulation - scientific basis, measurement and risk mitigation strategies, and first results

The Atlantic Meridional Overturning Circulation (MOC) carries up to one quarter of the global northward heat transport in the Subtropical North Atlantic. A system monitoring the strength of the MOC volume transport has been operating since April 2004. The core of this system is an array of moored sensors measuring density, bottom pressure and ocean currents. A strategy to mitigate risks of possible partial failures of the array is presented, relying on backup and complementary measurements. The MOC is decomposed into five components, making use of the continuous moored observations, and of cable measurements across the Straits of Florida, and wind stress data. The components compensate for each other, indicating that the system is working reliably. The year-long average strength of the MOC is 18.7±5.6 Sv, with wind-driven and density-inferred transports contributing equally to the variability. Numerical simulations suggest that the surprisingly fast density changes at the western boundary are partially linked to westward propagating planetary wave

Halcyornis toliapicus (aves: Lower Eocene, England) indicates advanced neuromorphology in Mesozoic Neornithes

Our recent X-ray micro computer-tomographic (μCT) investigations of Prophaethon shrubsolei and Odontopteryx toliapica from the Lower Eocene London Clay Formation of England revealed the avian brain to have been essentially modern in form by 55 Ma, but that an important vision-related synapomorphy of living birds, the eminentia sagittalis of the telencephalon, was poorly developed. This evidence suggested that the feature probably appeared close to the end of the Mesozoic. Here we use μCT analysis to describe the endocranium of Halcyornis toliapicus, also from the London Clay Formation. The affinities of Halcyornis have been hotly debated, with the taxon referred to the Charadriiformes (Laridae), Coraciiformes (Alcedinidae, and its own family Halcyornithidae) and most recently that Halcyornithidae may be a possible senior synonym of Pseudasturidae (Pan-Psittaciformes). Unlike Prophaethon and Odontopteryx, the eminentia sagittalis of Halcyornis is strongly developed and comparable to that of living species. Like those London Clay taxa, the eminentia sagittalis occupies a rostral position on the telencephalon. The senses of Halcyornis appear to have been well developed. The length of the cochlear duct of the inner ear indicates a hearing sensitivity within the upper range of living species, and enlarged olfactory lobes suggest a reasonable reliance on sense of smell. The optic nerves were especially well developed which, together with the strong development of the eminentia sagittalis, indicates a high degree of visual specialization in Halcyornis. The advanced development of the eminentia sagittalis further supports a Mesozoic age for the appearance of this structure and associated neural architectural complexity found in extant Aves. The eminentia sagittalis of living Psittaciformes is situated caudally on the telencephalon, making a Pan-Psittaciformes relationship unlikely for Halcyorni

The primary cosmic ray spectrum above 10 to the 19th power eV

Progress on a re-evaluation of the spectrum of cosmic rays determined with the Haverah Park shower array is described. Particular attention is paid to the reality of some giant showers

Modeling the power flow in normal conductor-insulator-superconductor junctions

Normal conductor-insulator-superconductor (NIS) junctions promise to be interesting for x-ray and phonon sensing applications, in particular due to the expected self-cooling of the N electrode by the tunneling current. Such cooling would enable the operation of the active element of the sensor below the cryostat temperature and at a correspondingly higher sensitivity. It would also allow the use of MS junctions as microcoolers. At present, this cooling has not been realized in large area junctions (suitable for a number of detector applications). In this article, we discuss a detailed modeling of the heat flow in such junctions; we show how the heat flow into the normal electrode by quasiparticle back-tunneling and phonon absorption from quasiparticle pair recombination can overcompensate the cooling power. This provides a microscopic explanation of the self-heating effects we observe in our large area NIS junctions. The model suggests a number of possible solutions