Spin glass behavior and magnetic boson peak in a structural glass of a magnetic ionic liquid.

Glassy magnetic behavior has been observed in a wide range of crystalline magnetic materials called spin glass. Here, we report spin glass behavior in a structural glass of a magnetic ionic liquid, C4mimFeCl4. Magnetization measurements demonstrate that an antiferromagnetic ordering occurs at TN = 2.3 K in the crystalline state, while a spin glass transition occurs at TSG = 0.4 K in the structural glass state. In addition, localized magnetic excitations were found in the spin glass state by inelastic neutron scattering, in contrast to spin-wave excitations in the ordered phase of the crystalline sample. The localized excitation was scaled by the Bose population factor below TSG and gradually disappeared above TSG. This feature is highly reminiscent of boson peaks commonly observed in structural glasses. We suggest the "magnetic" boson peak to be one of the inherent dynamics of a spin glass state.

Neutron visualization of inhomogeneous buried interfaces in thin films.

When designing some functions in thin film systems, one of the key concepts is the structure of the constituent layers and interfaces. In an actual system, the layers and interfaces are often inhomogeneous in different scales, from hundreds of microns to several nanometers, causing differences in properties, despite very similar average structures. In this case, the choice of the observation point is critical to clarify the problem. Another critical aspect is the identification of these points by surveying the entire inhomogeneous thin film system. This article presents a description of a novel promising solution that is suitable for nondestructive visualization of inhomogeneous buried layers and interfaces in thin films. Such observations have been impossible until now. In this investigation, a unique extension of neutron reflectometry is proposed. While conventional neutron reflectivity just gives average depth-profiling of the scattering length density of layered thin films, the present method provides full picture of the inhomogeneity. In general, achieving a high spatial-resolving power for neutron scattering is not straightforward because the neutron counts become fairly limited at the sample or the detector position when the beam size is reduced. As a result, XY scanning of a sample with a small neutron beam is fairly difficult because of the required long measurement time. To address these issues, new concepts have been introduced for neutron reflectivity. The proposed method uses a wide beam instead of reducing the beam size. In addition, it measures the projection reflection profile instead of the total integrated intensity. These profiles are collected at a set of different in-plane angles. Similar to computed tomography, it is possible to obtain the specimen's two-dimensional (2D) neutron reflectivity distribution as one image. Because the spatial resolution is limited by the detection method, a Hadamard coded mask is employed to measure the reflection projection with only 50% loss of the primary neutron intensity. When the time-of-flight (ToF) mode is used for the neutron experiment, one can obtain many images as a function of ToF, i.e., the wavevector transfer. Such series of images can be displayed as a video. This indicates that the neutron reflectivity profiles of local points can be retrieved from the above video images. This paper presents the first report on the development of neutron reflectivity with imaging capability, and the analysis of local points in inhomogeneous layered thin-films without utilizing a small neutron beam. In the present work, the feasibility of the proposed method with approximately 1 mm spatial resolution was examined. In addition, further improvements of the approach are discussed. It is anticipated that this technique will facilitate new opportunities in the study of buried function interfaces.

Effects of rumen-protected methionine on milk production in early lactation dairy cattle fed with a diet containing 14.5% crude protein.

We evaluated the influence on milk production of feeding early lactation cows a diet that included 14.5% crude protein (CP) and that did not meet methionine (Met) requirements or that met them by supplying rumen-protected Met (RPMet). Thirty-nine multiparous Holstein cows were allocated into two groups. For 15 weeks after calving, each group was fed one of the two total mixed rations, Control (n = 20) or Treatment (n = 19). The Treatment group received added RPMet at 0.034% (8 g/day) of the Control diet on dry matter basis. The adequacies of Met for the Control and Treatment groups were 96% and 106%, respectively, and for other amino acids, >110%. The CP level (14.5%) was 1 percentage point lower than that recommended by the Japanese Feeding Standard (2006). No between-group differences were found in milk yield (40 kg/day), milk composition, plasma profile, rumen fermentation, nitrogen balance, or cow health. Met intake and the amount of rumen-undegradable feed Met were higher in the Treatment group (p < 0.05). Microbial Met and total metabolizable Met did not differ between groups. Supplying RPMet in a 14.5% CP diet during early lactation did not dramatically affect milk production, because the amount of total metabolizable Met was unchanged.

A Novel Microemulsion Phase Transition: Toward the Elucidation of Third-Phase Formation in Spent Nuclear Fuel Reprocessing.

We present evidence that the transition between organic and third phases, which can be observed in the plutonium uranium reduction extraction (PUREX) process at high metal loading, is an unusual transition between two isotropic bicontinuous microemulsion phases. As this system contains so many components, however, we have been seeking first to investigate the properties of a simpler system, namely, the related metal-free, quaternary water/n-dodecane/nitric acid/tributyl phosphate (TBP) system. This quaternary system has been shown to exhibit, under appropriate conditions, three coexisting phases: a light organic phase, an aqueous phase, and the so-called third phase. In the current work, we focused on the coexistence of the light organic phase with the third phase. Using Gibbs ensemble Monte Carlo (GEMC) simulations, we found coexistence of a phase rich in nitric acid and dilute in n-dodecane (the third phase) with a phase more dilute in nitric acid but rich in n-dodecane (the light organic phase). The compositions and densities of these two coexisting phases determined using the simulations were in good agreement with those determined experimentally. Because such systems are generally dense and the molecules involved are not simple, the particle exchange rate in their GEMC simulations can be rather low. To test whether a system having a composition between those of the observed third and organic phases is indeed unstable with respect to phase separation, we used the Bennett acceptance ratio method to calculate the Gibbs energies of the homogeneous phase and the weighted average of the two coexisting phases, where the compositions of these phases were taken both from experimental results and from the results of the GEMC simulations. Both demixed states were determined to have statistically significant lower Gibbs energies than the uniform, mixed phase, providing confirmation that the GEMC simulations correctly predicted the phase separation. Snapshots from the simulations and a cluster analysis of the organic and third phases revealed structures akin to bicontinuous microemulsion phases, with the polar species residing within a mesh and with the surface of the mesh formed by amphiphilic TBP molecules. The nonpolar n-dodecane molecules were observed in these snapshots to be outside this mesh. The only large-scale structural differences observed between the two phases were the dimensions of the mesh. Evidence for the correctness of these structures was provided by the results of small-angle X-ray scattering (SAXS) studies, where the profiles obtained for both the organic and third phases agreed well with those calculated from simulations. Finally, we looked at the microscopic structures of the two phases. In the organic phase, the basic motif was observed to be one nitric acid molecule hydrogen-bonded to a TBP molecule. In the third phase, the most common structure was that of the hydrogen-bonded TBP-HNO3-HNO3 chain. A cluster analysis provided evidence for TBP forming an extended, connected network in both phases. Studies of the effects of metal ions on these systems will be presented elsewhere.

Comparative Molecular Dynamics Study on Tri-n-butyl Phosphate in Organic and Aqueous Environments and Its Relevance to Nuclear Extraction Processes.

A refined model for tri-n-butyl phosphate (TBP), which uses a new set of partial charges generated from our ab initio density functional theory calculations, has been proposed in this study. Molecular dynamics simulations are conducted to determine the thermodynamic properties, transport properties, and the microscopic structures of liquid TBP, TBP/water mixtures, and TBP/n-alkane mixtures. These results are compared with those obtained from four other TBP models, previously described in the literature. We conclude that our refined TBP model appears to be the only TBP model from this set that, with reasonable accuracy, can simultaneously predict the properties of TBP in bulk TBP, in organic diluents, and in aqueous solution. The other models only work well for two of the three systems mentioned above. This new TBP model is thus appropriate for the simulation of liquid-liquid extraction systems in the nuclear extraction process, where one needs to simultaneously model TBP in both aqueous and organic phases. It is also promising for the investigation of the microscopic structure of the organic phase in these processes and for the characterization of third-phase formation, where TBP again interacts simultaneously with both polar and nonpolar molecules. Because the proposed TBP model uses OPLS-2005 Lennard-Jones parameters, it may be used with confidence to model mixtures of TBP with other species whose parameters are given by the OPLS-2005 force field.

Investigation of substitution effect on fluorescence properties of Zn²âº-selective ratiometric fluorescent compounds: 2-(2'-Hydroxyphenyl)benzimidazole derivatives.

2-(2'-Hydroxyphenyl)benzimidazole derivatives (X-HBIs), modified by various substituents X (X=H, CH3, OH, OCH3, NO2, NHCOCH3, NH2, N(CH3)2), were synthesized and their fluorescent behaviors and equilibriums in aqueous solution were studied. Strong fluorescence attributed to the tautomer emission was observed in aqueous solution at pH 7.4. The fluorescence intensities of the X-HBIs were enhanced selectively by addition of Zn(2+) but not by addition of Na(+), K(+), Mg(2+), Ca(2+), Mn(2+), Fe(2+), Co(2+), Ni(2+), and Cu(2+). Additionally, the effective ratiometric fluorescence response to Zn(2+) addition was observed in 5-NH2-HBI and 5-N(Me)2-HBI. The pH-titration and speciation studies proved that the X-HBIs have two or three protonation equilibriums and one complexation equilibrium corresponding to the formation of the [Zn(X-HBI)](+) complex. Further structural studies using extended X-ray absorption fine structure analyses and density functional theory calculations identified the dominant Zn(2+) species as the [Zn(HBI)(H2O)3](+) complex in aqueous solution. Based on the substituent effect on the fluorescence properties of X-HBIs and their Zn(2+) complexes in aqueous solution, the maximum fluorescence excitation and fluorescence wavelengths of both the tautomeric form and the Zn(2+) complexes were dependent on the Hammett substituent constants of X, which was attributed to the change of the π-π* energy gap of HBI by introduction of the substituent.