Thermodynamics of Highly Interacting Blend PCHMA/dPS by TOF-SANS.

We investigate the thermodynamics of a highly interacting blend of poly(cyclohexyl methacrylate)/deuterated poly(styrene) (PCHMA/dPS) with small-angle neutron scattering (SANS). This system is experimentally challenging due to the proximity of the blend phase boundary (>200 °C) and degradation temperatures. To achieve the large wavenumber q-range and flux required for kinetic experiments, we employ a SANS diffractometer in time-of-flight (TOF) mode at a reactor source and ancillary microscopy, calorimetry, and thermal gravimetric analysis. Isothermal SANS data are well described by random-phase approximation (RPA), yielding the second derivative of the free energy of mixing (G″), the effective interaction (χ̅) parameter, and extrapolated spinodal temperatures. Instead of the Cahn-Hilliard-Cook (CHC) framework, temperature (T)-jump experiments within the one-phase region are found to be well described by the RPA at all temperatures away from the glass transition temperature, providing effectively near-equilibrium results. We employ CHC theory to estimate the blend mobility and G″(T) conditions where such an approximation holds. TOF-SANS is then used to precisely resolve G″(T) and χ̅(T) during T-jumps in intervals of a few seconds and overall timescales of a few minutes. PCHMA/dPS emerges as a highly interacting partially miscible blend, with a steep dependence of G″(T) [mol/cm3] = -0.00228 + 1.1821/T [K], which we benchmark against previously reported highly interacting lower critical solution temperature (LCST) polymer blends.

Uniaxial polarization analysis of bulk ferromagnets: theory and first experimental results.

On the basis of Brown's static equations of micromagnetics, the uniaxial polarization of the scattered neutron beam of a bulk magnetic material is computed. The approach considers a Hamiltonian that takes into account the isotropic exchange interaction, the antisymmetric Dzyaloshinskii-Moriya interaction, magnetic anisotropy, the dipole-dipole interaction and the effect of an applied magnetic field. In the high-field limit, the solutions for the magnetization Fourier components are used to obtain closed-form results for the spin-polarized small-angle neutron scattering (SANS) cross sections and the ensuing polarization. The theoretical expressions are compared with experimental data on a soft magnetic nanocrystalline alloy. The micromagnetic SANS theory provides a general framework for polarized real-space neutron methods, and it may open up a new avenue for magnetic neutron data analysis on magnetic microstructures.

Superchaotropic nano-ions as foam stabilizers.

HYPOTHESIS: Weakly hydrated nanometric ions, called superchaotropes, were recently shown to adsorb strongly to non-ionic surfaces affecting drastically the surface's physical-chemical properties due to a charging effect. Superchaotropic ions could serve as stabilizing agents for non-ionic colloidal systems, such as non-ionic surfactant foams. EXPERIMENTS: We study foams of the non-ionic surfactant BrijO10 (C18:1E10) without and in presence of the superchaotropic Keggin-ion SiW12O404- (SiW). The foams are investigated under free drainage conditions by image analysis and conductimetry to reveal the effect of SiW on the foam stability, liquid drainage, and bubble size. Additionally, small angle neutron scattering on the same foams, but in a dry quasi-stationary state, provides insight into effects of SiW on the foam films. FINDINGS: SiW strongly stabilizes non-ionic surfactant foams at millimolar concentrations by inducing electrostatic repulsions between foam film interfaces resulting in thicker and monodisperse foam films. A similar effect is observed with the ionic surfactant sodium dodecylsulfate (SDS) but to a lesser extent and with a different mechanism. At the foam films' interface, SiW adsorbs to the polar non-ionic surfactant heads driven by the superchaotropic effect whereas DS- anchors between non-ionic surfactant alkyl chains by the hydrophobic effect. The potential of superchaotropic ions as foam stabilizers is herein demonstrated.

Focusing and imaging of cold neutrons with a permanent magnetic lens.

This paper reports imaging of objects with slow neutrons, specifically very cold neutrons and cold neutrons, at Institut Laue Langevin, using novel, permanent magnet (Nd2Fe14B) compound refractive lenses (MCRL) with a large 2.5 cm bore diameter. The MCRL focuses and images spin-up neutrons and defocuses spin-down neutrons via a large, radial magnetic field gradient. A single lens neutron microscope, composed of an MCRL objective lens with 2-fold magnification, was tested using very cold (slow) neutrons at 45 Å wavelength. One-to-one imaging was obtained using 16.7 Å polarized neutrons. The magnetic field gradient of the MCRL was measured by raster-scanned pencil beams on D33. Finally, a compound neutron microscope was realized using an MCRL condenser lens, which provided increased illumination of objects, and an MCRL as objective lens to produce 3.5-fold magnification.

Disordered skyrmion phase stabilized by magnetic frustration in a chiral magnet.

Magnetic skyrmions are vortex-like topological spin textures often observed to form a triangular-lattice skyrmion crystal in structurally chiral magnets with the Dzyaloshinskii-Moriya interaction. Recently, ß-Mn structure-type Co-Zn-Mn alloys were identified as a new class of chiral magnet to host such skyrmion crystal phases, while ß-Mn itself is known as hosting an elemental geometrically frustrated spin liquid. We report the intermediate composition system Co7Zn7Mn6 to be a unique host of two disconnected, thermal-equilibrium topological skyrmion phases; one is a conventional skyrmion crystal phase stabilized by thermal fluctuations and restricted to exist just below the magnetic transition temperature Tc, and the other is a novel three-dimensionally disordered skyrmion phase that is stable well below Tc. The stability of this new disordered skyrmion phase is due to a cooperative interplay between the chiral magnetism with the Dzyaloshinskii-Moriya interaction and the frustrated magnetism inherent to ß-Mn.

Magnetic field-dependent spin structures of nanocrystalline holmium.

The results are reported of magnetic field-dependent neutron diffraction experiments on polycrystalline inert-gas condensed holmium with a nanometre crystallite size (D = 33 nm). At T = 50 K, no evidence is found for the existence of helifan(3/2) or helifan(2) structures for the nanocrystalline sample, in contrast with results reported in the literature for the single crystal. Instead, when the applied field H is increased, the helix pattern transforms progressively, most likely into a fan structure. It is the component of H which acts on the basal-plane spins of a given nanocrystallite that drives the disappearance of the helix; for nanocrystalline Ho, this field is about 1.3 T, and it is related to a characteristic kink in the virgin magnetization curve. For a coarse-grained Ho sample, concomitant with the destruction of the helix phase, the emergence of an unusual angular anisotropy (streak pattern) and the appearance of novel spin structures are observed.

Coconut Lethal Yellowing Diseases: A Phytoplasma Threat to Palms of Global Economic and Social Significance.

The recent discovery of Bogia coconut syndrome in Papua New Guinea (PNG) is the first report of a lethal yellowing disease (LYD) in Oceania. Numerous outbreaks of LYDs of coconut have been recorded in the Caribbean and Africa since the late Nineteenth century and have caused the death of millions of palms across several continents during the Twentieth century. Despite the severity of economic losses, it was only in the 1970s that the causes of LYDs were identified as phytoplasmas, a group of insect-transmitted bacteria associated with diseases in many other economically important crop species. Since the development of polymerase chain reaction (PCR) technology, knowledge of LYDs epidemiology, ecology and vectors has grown rapidly. There is no economically viable treatment for LYDs and vector-based management is hampered by the fact that vectors have been positively identified in very few cases despite many attempted transmission trials. Some varieties and hybrids of coconut palm are known to be less susceptible to LYD but none are completely resistant. Optimal and current management of LYD is through strict quarantine, prompt detection and destruction of symptomatic palms, and replanting with less susceptible varieties or crop species. Advances in technology such as loop mediated isothermal amplification (LAMP) for detection and tracking of phytoplasma DNA in plants and insects, remote sensing for identifying symptomatic palms, and the advent of clustered regularly interspaced short palindromic repeats (CRISPR)-based tools for gene editing and plant breeding are likely to allow rapid progress in taxonomy as well as understanding and managing LYD phytoplasma pathosystems.

Fipronil: environmental fate, ecotoxicology, and human health concerns.

Fipronil is a highly effective, broad-spectrum insecticide with potential value for the control of a wide range of crop, public hygiene, amenity, and veterinary pests. It can generally be applied at low to very low dose rates to achieve effective pest control. Application rates vary between 0.6 and 200 g a.i./ha, depending on the target pest and formulation. It belongs to the phenyl pyrazole or fiprole group of chemicals and is a potent disrupter of the insect central nervous system via interference with the gamma-aminobutyric acid (GABA-) regulated chloride channel. Fipronil degrades slowly on vegetation and relatively slowly in soil and in water, with a half-life ranging between 36 hr and 7.3 mon depending on substrate and conditions. It is relatively immobile in soil and has low potential to leach into groundwater. One of its main degradation products, fipronil desulfinyl, is generally more toxic than the parent compound and is very persistent. There is evidence that fipronil and some of its degradates may bioaccumulate, particularly in fish. Further investigation on bioaccumulation is warranted, especially for the desulfinyl degradate. The suitability of fipronil for use in IPM must be evaluated on a case-by-case basis. In certain situations, fipronil may disrupt natural enemy populations, depending on the groups and species involved and the timing of application. The indications are that fipronil may be incompatible with locust IPM; hence, this possibility requires further urgent investigation. It is very highly toxic to termites and has severe and long-lasting negative impacts on termite populations. It thus presents a long-term risk to nutrient cycling and soil fertility where termites are "beneficial" key species in these ecological processes. Its toxicity to termites also increases the risk to the ecology of habitats in which termites are a dominant group, due to their importance as a food source to many higher animals. This risk has been demonstrated in Madagascar, where two endemic species of lizard and an endemic mammal decline in abundance because of their food chain link to termites. Fipronil is highly toxic to bees (LD50 = 0.004 microgram/bee), lizards [LD50 for Acanthodactylus dumerili (Lacertidae) is 30 micrograms a.i./g bw], and gallinaceous birds (LD50 = 11.3 mg/kg for Northern bobwhite quail), but shows low toxicity to waterfowl (LD50 > 2150 mg/kg for mallard duck). It is moderately toxic to laboratory mammals by oral exposure (LD50 = 97 mg/kg for rats; LD50 = 91 mg/kg for mice). Technical fipronil is in toxicity categories II and III, depending on route of administration, and is classed as a nonsensitizer. There are indications of carcinogenic action in rats at 300 ppm, but it is not carcinogenic to female mice at doses of 30 ppm. The acute toxicity of fipronil varies widely even in animals within the same taxonomic groups. Thus, toxicological findings from results on standard test animals are not necessarily applicable to animals in the wild. Testing on local species seems particularly important in determining the suitability of fipronil-based products for registration in different countries or habitats and the potential associated risk to nontarget wildlife. Risk assessment predictions have shown that some fipronil formulations present a risk to endangered bird, fish, and aquatic and marine invertebrates. Great care should thus be taken in using these formulations where they may impact any of these endangered wildlife groups. Work in Madagascar has highlighted field evidence of this risk. The dose levels at which fipronil produces thyroid cancer in rats are very high and are unlikely to occur under normal conditions of use. There is also dispute as to whether this is relevant to human health risk. However, as fipronil is a relatively new insecticide that has not been in use for long enough to evaluate the risk it may pose to human health, from data on human exposure to the product, a precautionary approach may be warranted. The use of some fipronil-based products on domestic animals is not recommended where handlers spend significant amounts of time grooming or handling treated animals. In general, it would appear unwise to use fipronil-based insecticides without accompanying environmental and human health monitoring, in situations, regions, or countries where it has not been used before, and where its use may lead to its introduction into the wider environment or bring it into contact with people. Further work is needed on the impacts of fipronil on nontarget vertebrate fauna (amphibians, reptiles, birds, and mammals) in the field before the risk to wildlife from this insecticide can be adequately validated. Further field study of the effects of fipronil on the nutrient cycling and soil water-infiltration activities of beneficial termites is required to assess the ecological impacts of the known toxicity of fipronil to these insects.

Characterization of polybutadiene-poly(ethyleneoxide) aggregates in aqueous solution: a light-scattering and small-angle neutron-scattering study.

For diblockcopolymers of polybutadiene-poly(ethyleneoxide) (PB-PEO) type, water is a selective solvent. In dependence of the length of both blocks and the block length ratio, these polymers form a multitude of self-assembled structures in solution. In the present work scattering methods are used to investigate the water-soluble polymer PB125-PEO155 . It is found to form long rodlike micelles, which are characterized with respect to the aggregate length L , the cross sectional radius RCS , the radial scattering length density profile sigma r, and the radial aggregation number Nrad. Model-independent as well as model-based approaches are used for the scattering data analysis. From dynamic light scattering (DLS) and static light scattering (SLS) experiments the weight averaged length Lw of these stiff elongated aggregates is determined to Lw=350 nm . Small angle neutron scattering (SANS) reveals a cross sectional radius of RCS=17 nm and in combination with results from the SLS the radial aggregation number is found to be Nrad=70 .

Persistence length of titin from rabbit skeletal muscles measured with scattering and microrheology techniques.

The persistence length of titin from rabbit skeletal muscles was measured using a combination of static and dynamic light scattering, and neutron small angle scattering. Values of persistence length in the range 9-16 nm were found for titin-II, which corresponds to mainly physiologically inelastic A-band part of the protein, and for a proteolytic fragment with 100-nm contour length from the physiologically elastic I-band part. The ratio of the hydrodynamic radius to the static radius of gyration indicates that the proteins obey Gaussian statistics typical of a flexible polymer in a -solvent. Furthermore, measurements of the flexibility as a function of temperature demonstrate that titin-II and the I-band titin fragment experience a similar denaturation process; unfolding begins at 318 K and proceeds in two stages: an initial gradual 50% change in persistence length is followed by a sharp unwinding transition at 338 K. Complementary microrheology (video particle tracking) measurements indicate that the viscoelasticity in dilute solution behaves according to the Flory/Fox model, providing a value of the radius of gyration for titin-II (63 +/- 1 nm) in agreement with static light scattering and small angle neutron scattering results.

PNIPAM-co-polystyrene core-shell microgels: structure, swelling behavior, and crystallization.

The present contribution presents the single-step preparation and characterization of poly(N-isopropyl acrylamide)-co-polystyrene core-shell microgels with varying polystyrene content. The swelling behavior of the particles is investigated using dynamic light scattering and differs significantly from the swelling behavior of poly(N-isopropyl acrylamide) homopolymer particles. The lower critical solution temperature is found to be shifted to lower temperatures upon increasing the polystyrene content of the particles. The core-shell structure of the particles is revealed by means of small angle neutron scattering (SANS) using the method of contrast variation. Additionally, the formation of mesoscopic crystals of these particles is investigated by means of scanning electron microscopy and also by SANS. The particles seem to have preferable properties with respect to crystallization compared to homopolymer microgels.

Hexagonal and square flux line lattices in CeCoIn5.

Using small-angle neutron scattering, we have imaged the magnetic flux line lattice (FLL) in the d-wave heavy-fermion superconductor CeCoIn5. At low fields we find a hexagonal FLL. Around 0.6 T this undergoes what is most likely a first-order transition to square symmetry, with the nearest neighbors oriented along the gap node directions. This orientation of the square FLL is consistent with theoretical predictions based on the d-wave order parameter symmetry.