Interaction of hydrated metals with chemically modified hexagonal boron nitride quantum dots: wastewater treatment and water splitting.

The electronic and adsorption properties of chemically modified square hexagonal boron nitride quantum dots are investigated using density functional theory calculations. The free energy and frequency calculations show that all the boron nitride flakes are stable before/after modification and metal adsorption. Edge modification significantly enhances the stability and interactivity of the flake. For instance, the free energy of binding decreases from -6.5 eV in the hydrogenated flake to -7.1 eV in the pristine one and the dipole moment increases from 4.5 D to 53.7 D, respectively. A wide spectrum of band gaps can also be achieved, where the band gap can be smoothly varied from ∼6 eV in edge fluorinated flakes to 0.2 in sulfurated ones. Six hydrated metals, Cd, Co, Cr, Cu, Fe, and Zn, are considered for adsorption by the flakes. The transition metals are highly selected by the flakes while heavy metals are weakly adsorbed. All hydrated metals are physically adsorbed by the edge and surface of hydrogenated flakes except Cu, which is chemically adsorbed. Chemical groups or elements attached to the flake strongly enhance the adsorption strength; the adsorption energy of hydrated Cr on the surface increases from 0.6 eV to 8.6 eV after attaching two COOH groups to the surface. Hydrogen evolution has also been observed through the adsorption process. The calculated low overpotential for the oxygen evolution reaction (0.52 V) and hydrogen adsorption strength (0.11 eV) for the hydrogen evolution reaction indicate that boron nitride quantum dots are not only potential candidates for the removal of different metals from wastewater but also for efficient water splitting.

Slater Insulator in Iridate Perovskites with Strong Spin-Orbit Coupling.

The perovskite SrIrO_{3} is an exotic narrow-band metal owing to a confluence of the strengths of the spin-orbit coupling (SOC) and the electron-electron correlations. It has been proposed that topological and magnetic insulating phases can be achieved by tuning the SOC, Hubbard interactions, and/or lattice symmetry. Here, we report that the substitution of nonmagnetic, isovalent Sn^{4+} for Ir^{4+} in the SrIr_{1-x}Sn_{x}O_{3} perovskites synthesized under high pressure leads to a metal-insulator transition to an antiferromagnetic (AF) phase at T_{N}≥225 K. The continuous change of the cell volume as detected by x-ray diffraction and the λ-shape transition of the specific heat on cooling through T_{N} demonstrate that the metal-insulator transition is of second order. Neutron powder diffraction results indicate that the Sn substitution enlarges an octahedral-site distortion that reduces the SOC relative to the spin-spin exchange interaction and results in the type-G AF spin ordering below T_{N}. Measurement of high-temperature magnetic susceptibility shows the evolution of magnetic coupling in the paramagnetic phase typical of weak itinerant-electron magnetism in the Sn-substituted samples. A reduced structural symmetry in the magnetically ordered phase leads to an electron gap opening at the Brillouin zone boundary below T_{N} in the same way as proposed by Slater.

Anisotropic two-dimensional electron gas at the LaAlO3/SrTiO3 (110) interface.

The observation of a high-mobility two-dimensional electron gas between two insulating complex oxides, especially LaAlO3/SrTiO3, has enhanced the potential of oxides for electronics. The occurrence of this conductivity is believed to be driven by polarization discontinuity, leading to an electronic reconstruction. In this scenario, the crystal orientation has an important role and no conductivity would be expected, for example, for the interface between LaAlO3 and (110)-oriented SrTiO3, which should not have a polarization discontinuity. Here we report the observation of unexpected conductivity at the LaAlO3/SrTiO3 interface prepared on (110)-oriented SrTiO3, with a LaAlO3-layer thickness-dependent metal-insulator transition. Density functional theory calculation reveals that electronic reconstruction, and thus conductivity, is still possible at this (110) interface by considering the energetically favourable (110) interface structure, that is, buckled TiO2/LaO, in which the polarization discontinuity is still present. The conductivity was further found to be strongly anisotropic along the different crystallographic directions with potential for anisotropic superconductivity and magnetism, leading to possible new physics and applications.

Long-range spin current driven by superconducting phase difference in a josephson junction with double layer ferromagnets.

We theoretically study spin current through ferromagnet (F) in a Josephson junction composed of s-wave superconductors and two layers of ferromagnets. Using quasiclassical theory, we show that the long-range spin current can be driven by the superconducting phase difference without a voltage drop. The origin of this spin current is due to spin-triplet Cooper pairs (STCs) formed by electrons of equal spin, which are induced by the proximity effect inside the F. We find that the spin current carried by the STCs exhibits long-range propagation in the F even where the Josephson charge current is practically zero. We also show that this spin current persists over a remarkably longer distance than the ordinary spin current carried by spin polarized conduction electrons in the F. Our results thus indicate the promising potential of Josephson junctions based on multilayer ferromagnets for spintronics applications with long-range propagating spin current.

Charge transfer in heterostructures of strongly correlated materials.

In this work, recent theoretical investigations by the authors in the area of oxide multilayers are briefly reviewed. The calculations were carried out using model Hamiltonians and a variety of non-perturbative techniques. Moreover, new results are also included here. They correspond to the generation of a metallic state by mixing insulators in a multilayer geometry, using the Hubbard and double-exchange models. For the latter, the resulting metallic state is also ferromagnetic. This illustrates how electron or hole doping via transfer of charge in multilayers can lead to the study of phase diagrams of transition metal oxides in the clean limit. Currently, these phase diagrams are much affected by the disordering standard chemical doping procedure, which introduces quenched disorder in the material.

Role of strong correlation in the recent angle-resolved photoemission spectroscopy experiments on cuprate superconductors.

Motivated by recent photoemission experiments on cuprates, the low-lying excitations of a strongly correlated superconducting state are studied numerically. It is observed that along the nodal direction these low-lying one-particle excitations show a linear momentum dependence for a wide range of excitation energies and, thus, they do not present a kinklike structure. The nodal Fermi velocity v(F), as well as other observables, are systematically evaluated directly from the calculated dispersions, and they are found to compare well with experiments. It is argued that the parameter dependence of v(F) is quantitatively explained by a simple picture of a renormalized Fermi velocity.

Resonating valence bond wave function for the two-dimensional fractional spin liquid.

The unconventional low-lying spin excitations, recently observed in neutron scattering experiments on Cs2CuCl4, are explained with a spin liquid wave function. The dispersion relation as well as the wave vector of the incommensurate spin correlations are well reproduced within a projected BCS wave function with gapless and fractionalized spin-1/2 excitations around the nodes of the BCS gap function. The proposed wave function is shown to be very accurate for one-dimensional spin-1/2 systems and remains similarly accurate in the two-dimensional model corresponding to Cs2CuCl4, thus representing a good ansatz for describing spin fractionalization in two dimensions.

Possible path to a new class of ferromagnetic and half-metallic ferromagnetic materials.

We introduce a path to a possibly new class of magnetic materials whose properties are determined entirely by the presence of a low concentration of specific point defects. Using model Hamiltonian and ab initio band structure methods we demonstrate that even large band gap nonmagnetic materials as simple as CaO with a small concentration of Ca vacancies can exhibit extraordinary properties. We show that such defects will initially bind the introduced charge carriers at neighboring sites and depending on the internal symmetry of the clusters so formed, will exhibit "local" magnetic moments which for concentrations as low as 3% transform this nonmagnetic insulator into a half-metallic ferromagnet.

Dietary gamma-linolenic acid dose-dependently modifies fatty acid composition and immune parameters in rats.

gamma-linolenic acid (GLA) has been reported to improve several inflammatory disorders through regulation of eicosanoid production. However, since GLA is a precursor of arachidonic acid, it may bring about increasing tissue arachidonic acid levels with subsequent pro-inflammatory events. To explore this possibility, we examined the effect of high-dose GLA acid on the fatty acid profile of immune cells, leukotriene B4 production by peritoneal exudate cells and immunoglobulin productivity of mesenteric lymph node lymphocytes of Sprague-Dawley rats. Male rats were fed 10% fat diets containing graded levels, 0, 20, 40 and 60% of GLA for 3 weeks. The results showed the distinction in activity of metabolizing GLA between immune cells and liver. Thus, in immune cells such as mesenteric lymph node and spleen lymphocytes and peritoneal exudate cells, more dihomo-gamma-linolenic acid was found than in the liver. Leukotriene B4 production by peritoneal exudate cells was significantly suppressed when fed the highest level of GLA suggesting a lower risk of allergic reaction. Moreover, immunoglobulin productivity in mesenteric lymph node lymphocytes was promoted by dietary GLA. The present study indicates that a high dose of GLA may exert anti-inflammatory effects through suppression of leukotriene B4 release and strengthening of gut immune system, thus ameliorating allergic reaction.

Interactions of dietary fats and proteins on fatty acid composition of immune cells and LTB4 production by peritoneal exudate cells of rats.

The interaction of dietary fats and proteins on lipid parameters of rats was studied using safflower oil (linoleic acid-rich), borage oil (gamma-linolenic acid-rich) or perilla oil (alpha-linolenic acid-rich) in combination with casein or soybean protein. The experiment was focused on the fatty acid composition of immune cells and the leukotriene B4 production by peritoneal exudate cells. Serum total cholesterol, triglyceride, and phospholipid levels were low in perilla oil-fed or soybean protein-fed rats. Fatty acid compositions of serum and liver phospholipids reflected those of dietary fats. However, feeding borage oil resulted in a marked increase in the proportion of dihomo-gamma-linolenic acid in phospholipids of peritoneal exudate cells, spleen lymphocytes, and mesenteric lymph node lymphocytes in relation to those of liver and serum. It is suggested that activities of metabolic n-6 polyunsaturated fatty acids are different between immune and other tissues. In addition, the magnitude of the reduction of the proportion of linoleic acid of perilla oil in immune cells was considerably more moderate than serum and liver, indicating a different degree of interference of alpha-linolenic acid with linoleic acid metabolism. Leukotriene release from peritoneal exudate cells was in the order of safflower oil > borage oil > perilla oil groups as reflecting the proportion of arachidonic acid, and tended to be lower in soybean protein-fed groups. These suggest an anti-inflammatory property of gamma-linolenic acid as well as alpha-linolenic acid tended to be strengthened when they were combined with soybean protein than with casein.

Interactions of Dietary Fats and Proteins on Fatty Acid Composition of Immune Cells and LTB4 Production by Peritoneal Exudate Cells of Rats.

The interaction of dietary fats and proteins on lipid parameters of rats was studied using safflower oil (linoleic acid-rich), borage oil (γ-linolenic acid-rich) or perilla oil (α-linolenic acid-rich) in combination with casein or soybean protein. The experiment was focused on the fatty acid composition of immune cells and the leukotriene B4 production by peritoneal exudate cells. Serum total cholesterol, triglyceride, and phospholipid levels were low in perilla oil-fed or soybean protein-fed rats. Fatty acid compositions of serum and liver phospholipids reflected those of dietary fats. However, feeding borage oil resulted in a marked increase in the proportion of dihomo-γ-linolenic acid in phospholipids of peritoneal exudate cells, spleen lymphocytes, and mesenteric lymph node lymphocytes in relation to those of liver and serum. It is suggested that activities of metabolic n-6 polyunsaturated fatty acids are different between immune and other tissues. In addition, the magnitude of the reduction of the proportion of linoleic acid of perilla oil in immune cells was considerably more moderate than serum and liver, indicating a different degree of interference of α-linolenic acid with linoleic acid metabolism. Leukotriene B4 release from peritoneal exudate cells was in the order of safflower oil>borage oil>perilla oil groups as reflecting the proportion of arachidonic acid, and tended to be lower in soybean protein-fed groups. These suggest an anti-inflammatory property of γ-linolenic acid as well as α-linolenic acid tended to be strengthened when they were combined with soybean protein than with casein.

Ferromagnetic, A-type, and charge-ordered CE-type states in doped manganites using jahn-teller phonons

The two-orbital model for manganites with both noncooperative and cooperative Jahn-Teller phonons is studied at hole density x = 0.5 using Monte Carlo techniques. The phase diagram is obtained by varying the electron-phonon coupling and the t(2g)-spins exchange. The insulating CE-type charge- and orbital-ordered state with the z-axis charge stacking observed in narrow-bandwidth manganites is stabilized in the simulations. Its charge gap Delta(CO) is much larger than the critical temperature k(B)T(CO). Metalliclike A-type and ferromagnetic states are also obtained in the same framework, and the phase boundaries among them have first-order characteristics.

Magnetic domains and stripes in a spin-fermion model for cuprates

Monte Carlo simulations applied to a model of interacting fermions and classical spins show the existence of antiferromagnetic spin domains and charge stripes upon hole doping. The stripes have a filling of approximately 1/2 hole per site, and they separate spin domains with a pi phase shift among them. The observed stripes run either along the x or y axes. No particular boundary conditions or external fields are needed to stabilize these structures. When magnetic incommensurate peaks are observed at momentum pi(1,1-delta), charge incommensurate peaks appear at (0,2delta). The charge fluctuations responsible for the stripe formation also induce a pseudogap in the density of states.

Giant cluster coexistence in doped manganites and other compounds

Computational studies of models for manganese oxides show the generation of large coexisting metallic and insulating clusters with equal electronic density, in agreement with the recently discovered micrometer-sized inhomogeneities in manganites. The clusters are induced by disorder on exchange and hopping amplitudes near first-order transitions of the nondisordered strongly coupled system. The random-field Ising model illustrates the qualitative aspects of our results. Percolative characteristics are natural in this context. The conclusions are general and apply to a variety of compounds.

Inhibition by dietary tea polyphenols of chemical mediator release from rat peritoneal exudate cells.

Male Wistar rats were given purified diets containing safflower (SAF), perilla (PER), or palm (PAL) oils with or without 1% tea polyphenols (TP) for 3 weeks, and chemical mediator releasing activity from rat peritoneal exudate cells (PEC) was measured. Histamine releasing activity was not influenced by TP, while histamine release and intracellular histamine content were significantly increased in the PAL-fed group. On the contrary, leukotriene B4 (LTB4) release was significantly lower in rats fed PER than in those fed SAF and PAL, and TP significantly decreased the release in all fat groups. TP also significantly inhibited the release of LTB5, which was generated only in rats fed PER. TP significantly decreased the proportion of arachidonic acid (AA) in PEC in the SAF-fed group and that of eicosapentaenoic acid (EPA), the precursor of LTB5 in the PER-fed group, but did not influence that of AA in the PAL- and PER-fed group. These results suggest that ingestion of TP improves type I allergic symptom through the inhibition of LT release though the inhibition by TP could not be totally explained by the reduction of substrate fatty acid.

Dietary effects of eicosapentaenoic and docosahexaenoic acid esters on lipid metabolism and immune parameters in Sprague-Dawley rats.

Sprague-Dawley rats were fed eicosapentaenoic (EPA) and docosahexaenoic acid (DHA) ethyl esters at the 2% level for 3 weeks to clarify their effects on immune functions. In the rats fed EPA or DHA, serum cholesterol, triglyceride, and phospholipid (PL) levels were significantly lower than those in the rats fed safflower oil. In PL fractions of serum, liver, lung, splenocytes, and peritoneal exudate cells (PEC), increases in linoleic and dihomo-gamma-linolenic acid contents and a decrease in arachidonic acid (AA) content were observed in the rats fed EPA or DHA. In addition, the EPA content increased in the rats fed EPA and DHA. In the rats fed EPA or DHA, a decrease of LTB4 productivity and an increase of LTBs productivity were observed in the PEC, in response to the treatment with 5 microM calcium ionophore A23187 for 20 min. The changes in leukotriene production were more marked in EPA-fed rats than in DHA-fed rats. These results suggest that dietary EPA affects lipid metabolism and leukotriene synthesis more strongly than DHA.

Effect of dietary antioxidants on serum lipid contents and immunoglobulin productivity of lymphocytes in Sprague-Dawley rats.

Sprague-Dawley rats were fed alpha-tocopherol, tocotrienol, or quercetin to examine their dietary effects on serum lipid contents and immunoglobulin productivity. In tocotrienol or quercetin groups, serum triglyceride was lower than in the none group. Moreover, in the alpha-tocopherol group, serum IgA level and IgA productivity of MLN lymphocytes were high, while in the tocotrienol group, IgM productivity of spleen lymphocytes and IgA, IgG, and IgM productivity of MLN lymphocytes were high. Thus, we suggested each antioxidant had different effects in rats.

Phase separation scenario for manganese oxides and related materials

Recent computational studies of models for manganese oxides have revealed a rich phase diagram, which was not anticipated in early calculations in this context performed in the 1950s and 1960s. In particular, the transition between the antiferromagnetic insulator state of the hole-undoped limit and the ferromagnetic metal at finite hole density was found to occur through a mixed-phase process. When extended Coulomb interactions are included, a microscopically charged inhomogeneous state should be stabilized. These phase separation tendencies, also present at low electronic densities, influence the properties of the ferromagnetic region by increasing charge fluctuations. Experimental data reviewed here by applying several techniques for manganites and other materials are consistent with this scenario. Similarities with results previously discussed in the context of cuprates are clear from this analysis, although the phase segregation tendencies in manganites appear stronger.

Dietary effect of EPA-rich and DHA-rich fish oils on the immune function of Sprague-Dawley rats.

The dietary effect of fish oils (FOs) rich in eicosapentaenoic acid (EPA) or docosahexaenoic acid (DHA) on the immune function of Sprague-Dawley rats was compared with that of safflower oil. After 3 weeks of feeding at the 10% level of a dietary fat, the IgG and IgM production by splenocytes and IgG production by mesenteric lymph node (MLN) lymphocytes were significantly higher in the FO-fed rats, while no significant difference was found in IgA or IgE productivity by both the spleen and MLN lymphocytes. In the FO-fed rats, peritoneal exudate cells released a lower amount of LTB4, reflecting their lower arachidonic acid level, and a higher amount of LTB5, reflecting their higher EPA level in phospholipids. On these EPA-rich FO exerted a stronger effect than DHA-rich FO immune functions.

Combined therapy with interleukin 2 and indomethacin in mice inoculated with MH134 hepatoma.

The antitumor effects of indomethacin and interleukin 2 (IL-2) were studied in C3H/HeJ mice inoculated with MH134 hepatoma cells. Combined treatment with indomethacin and IL-2 augmented natural killer (NK) cells in mice with MH134-induced peritoneal carcinomatosis, and the survival of the treated mice was significantly longer than the non-treated mice. In animals with subcutaneous MH134 tumors, the combined therapy with indomethacin and IL-2 significantly suppressed tumor growth and induced complete regression of the tumor in three out of five mice. These results suggest that indomethacin and IL-2 therapy could be effective on human gastrointestinal cancer cells as well.