Angle-resolved photoemission spectroscopy of electron-doped cuprate superconductors: isotropic electron-phonon coupling

We have performed high resolution angle-resolved photoemission (ARPES) studies on electron-doped cuprate superconductors Sm2-xCexCuO4 (x=0.10, 0.15, 0.18), Nd2-xCexCuO4 (x=0.15), and Eu2-xCexCuO4 (x=0.15). Imaginary parts of the electron removal self energy show steplike features due to an electron-bosonic mode coupling. The steplike feature is seen along both nodal and antinodal directions but at energies of 50 and 70 meV, respectively, independent of the doping and rare earth element. Such energy scales can be understood as being due to preferential coupling to half- and full-breathing mode phonons, revealing the phononic origin of the kink structures. Estimated electron-phonon coupling constant lambda from the self energy is roughly independent of the doping and momentum. The isotropic nature of lambda is discussed in comparison with the hole-doped case where a strong anisotropy exists.     

Thermotropic Compounds with Two Terminal Mesogenic Units and a Central Spacer. 51. Homologous Series of Polymethylene-α, ω-Bis (p-Oxybenzylidene Aniline)

Two series of new thermotropic compounds with two terminal mesogenic units, p-oxybenzylidene-p-substituted anilines, attached to both ends of a central polymethylene spacer were prepared. The first series of compounds has central polymethylene spacers of varying length, while the second has different substituents on the aniline moiety of the mesogenic groups which are bracketing the central decamethylene spacer. The mesomorphic properties of the compounds were investigated by differential scanning calorimetry and on the hot-stage of a polarizing microscope. A thermodynamic analysis of the phase transitions of the compounds was made and the results are explained in relation to their structure.     

Diffusion of chromium in chrysoberyl

Cr³⁺ diffusion in chrysoberyl (BeAl₂O₄) irradiated by H⁺ ions and electrons has been studied and compared with diffusion in non-irradiated samples. Chrysoberyl crystals were irradiated with 6 MeV H⁺ ions to fluencies of 1×10¹⁶ cm^–2 for 25 min and with 10 MeV electrons to fluencies of 2×10¹⁷ cm^–2 for 1 h. Three different types of samples, which were doped with Cr³⁺, were annealed in horizontal alumina tube furnaces by 50 K intervals in the temperature range from 1773 to 1923 K for 200 h. Scanning electron microscope–energy dispersive X-ray spectrometer (SEM–EDX) was used to measure the diffusion. Arrhenius equations for the diffusion coefficient for Cr³⁺ in the temperature range 1773–1923 K were developed:     

Role of aromatic side chains in the folding and thermodynamic stability of integral membrane proteins

Aromatic residues are frequently found in helical and beta-barrel integral membrane proteins enriched at the membrane-water interface. Although the importance of these residues in membrane protein folding has been rationalized by thermodynamic partition measurements using peptide model systems, their contribution to the stability of bona fide membrane proteins has never been demonstrated. Here, we have investigated the contribution of interfacial aromatic residues to the thermodynamic stability of the beta-barrel outer membrane protein OmpA from Escherichia coli in lipid bilayers by performing extensive mutagenesis and equilibrium folding experiments. Isolated interfacial tryptophanes contribute -2.0 kcal/mol, isolated interfacial tyrosines contribute -2.6 kcal/mol, and isolated interfacial phenylalanines contribute -1.0 kcal/mol to the stability of this protein. These values agree well with the prediction from the Wimley-White interfacial hydrophobicity scale, except for tyrosine residues, which contribute more than has been expected from the peptide models. Double mutant cycle analysis reveals that interactions between aromatic side chains become significant when their centroids are separated by less than 6 A but are nearly insignificant above 7 A. Aromatic-aromatic side chain interactions are on the order of -1.0 to -1.4 kcal/mol and do not appear to depend on the type of aromatic residue. These results suggest that the clustering of aromatic side chains at membrane interfaces provides an additional heretofore not yet recognized driving force for the folding and stability of integral membrane proteins.     

Association of Paraoxonase 1 (PON1) polymorphisms with osteoporotic fracture risk in postmenopausal Korean women

There is increasing evidence of a biochemical link between lipid oxidation and bone metabolism. Paraoxonase 1 (PON1) prevents the oxidation of low-density lipoprotein (LDL) and metabolizes biologically active phospholipids in oxidized LDLs. Here, we performed association analyses of genetic variation in PON1 to ascertain its contribution to osteoporotic fractures (OFs) and bone mineral density (BMD). We directly sequenced the PON1 gene in 24 Korean individuals and identified 26 sequence variants. A large population of Korean postmenopausal women (n=1,329) was then genotyped for eight selected PON1 polymorphisms. BMD at the lumbar spine and femoral neck was measured using dual-energy X-ray absorptiometry. Lateral thoracolumbar (T4-L4) radiographs were obtained for vertebral fracture assessment, and the occurrence of non-vertebral fractures (i.e., wrist, hip, forearm, humerus, rib, and pelvis) was examined using self-reported data. Multivariate analyses showed that none of the polymorphisms was associated with BMD at either site. However, +5989A>G and +26080T>C polymorphisms were significantly associated with non-vertebral and vertebral fractures, respectively, after adjustment for covariates. Specifically, the minor allele of +5989A>G exerted a highly protective effect against non-vertebral fractures (OR=0.59, P=0.036), whereas the minor allele of +26080T>C was associated with increased susceptibility to vertebral fractures (OR=1.73, P=0.020). When the risk for any OFs (i.e., vertebral or non-vertebral) was considered, the statistical significance of both polymorphisms persisted (P=0.002-0.010). These results suggest that PON1 polymorphisms could be one of useful genetic markers for OF risk in postmenopausal women.     

Coordination Compounds of Schiff-Base Ligands Derived from Diaminomaleonitrile (DMN): Mononuclear, Dinuclear, and Macrocyclic Derivatives

Copper(II) and V(IV)O complexes of an open chain (1:2) Schiff-base ligand (H(2)L1), derived by the template condensation of diaminomaleonitrile (DMN) and salicylaldehyde, and dicopper(II) complexes of (2:2) macrocyclic Schiff-base ligands derived by template condensation of diformylphenols and diaminomaleonitrile, have been synthesized and studied. Structures have been established for the first time for mononuclear Cu(II) and V(IV)O derivatives of the open chain ligand H(2)L1 (1:2), a dinuclear macrocyclic Cu(II) complex derived from a 2:2 macrocyclic ligand (H(2)M1), and the half-condensed 1:1 salicylaldehyde ligand (H(2)L2). [Cu(L1)] (1) (L1 = C(18)H(10)N(4)O(2)) crystallized in the monoclinic system, space group P2(1)/n (No. 14), with a = 11.753(6) ?, b = 7.708(5) ?, c = 16.820(1) ?, and Z = 4. [VO(L1)(DMSO] (2) crystallized in the orthorhombic system, space group Pbca (No. 61), with a = 22.534(9) ?, b = 23.31(1) ?, c = 7.694(5) ?, and Z = 8. H(2)L2 (C(18)H(8)N(4)O) (3) crystallized in the monoclinic system, space group P2(1)/c (No. 14), with a = 13.004(6) ?, b = 11.441(7) ?, c = 7.030(4) ?, and Z = 4. [Cu(2)(M3)](CH(3)COCH(3)) (4) (M3 = C(32)H(24)N(8)O(4)) crystallized in the monoclinic system, space group C2/c (No. 15), with a = 38.33(2) ?, b = 8.059(4) ?, c = 22.67(2) ?, and Z = 8. [Cu(L3)(DMSO)] (5) (L3 = C(20)H(14)N(2)O(4)) crystallized in the triclinic system, space group P&onemacr; (No. 2), with a = 10.236(4) ?, b = 13.514(4) ?, c = 9.655(4) ?, and Z = 2. 4 results from the unique addition of two acetone molecules to two imine sites in [Cu(2)(M1)](ClO(4))(2) (M1 = 2:2 macrocyclic ligand derived from template condensation of DMN and 2,6-diformyl-4-methylphenol). 4 has extremely small Cu-OPh-Cu bridge angles (92.0, 92.8 degrees ), well below the expected lower limit for antiferromagnetic behavior, but is still antiferromagnetically coupled (-2J = 25.2 cm(-)(1)). This behavior is associated with a possible antiferromagnetic exchange term that involves the conjugated framework of the macrocyclic ligand itself. The ligand L3 in 5 results from hydrolysis of M1 on recrystallization of [Cu(2)(M1)](ClO(4))(2) from undried dimethyl sulfoxide.     

Label-free emission assay of mercuric ions using DNA duplexes of poly(dT)

In this study, an assay to quantify the presence of mercuric ions and methyl mercury by double-stranded DNA containing a poly(dT) sequence was developed using a light switch compound, Ru(phen)(2)(dppz)(2+) (1), which is known to intercalate into double-stranded DNA. Upon treatment with mercuric ions, the metal-to-ligand charge transfer (MLCT) emission derived from the intercalation of 1 was reduced due to the formation of DNA duplexes containing T-Hg(2+)-T base pairs by the dehybridization of poly(dT)-poly(dA) duplexes at room temperature. As the concentration of Hg(2+) was increased, the emission of 1 gradually decreased. This label-free method had a detection limit of 5 nM. Other metal ions, such as K(+), Ag(+), Ca(2+), Mg(2+), Zn(2+), Mn(2+), Co(2+), Ni(2+), Cu(2+), Cd(2+), Cr(3+), Fe(3+), had no significant effect on reducing emission. This emission method can differentiate matched and mismatched poly(dT) sequences based on the dehybridization rate of dsDNA and the rate decreased in the order of T(10)C·A(11)～ T(10)A·A(11) > T(10)G·A(11) > T(11)·A(11).     

Color tunability of nanophosphors by changing cations for solid-state lighting

X₃MgSi₂O₈: Eu²⁺, Mn²⁺ (X=Ba, Sr, Ca) phosphors with the mean particle size of 200 nm and the spherical shape are synthesized through combustion method. They show three emission colors under near-ultraviolet light: the blue and green colors from Eu²⁺ ions and the red color from Mn²⁺ ions. Three emission bands show the different emission colors with changing X²⁺ cations. These color shifts are discussed in terms of two competing factors of the crystal field strength and the covalency. These phosphors with maximum excitation of around 375 nm can be applied as color-tunable phosphors for white-light-emitting diode based on ultraviolet/phosphor technology.     

Effect of chemical structure on the crosslinking behavior of bismaleimides: Rheological study

The effect of molecular structure on the cure characteristics of bismaleimides (BMIs) was investigated by rheological measurements. BMI resins of different chemical structures were used, prepared from diglycidyl ether of bisphenol A and N-(3-carboxy phenyl) maleimide or N-(4-carboxy phenyl) maleimide. Temperature dependence of the rheological data was correlated to the Arrhenius equation, from which the activation energy of crosslinking was calculated.Upon heating in dynamic curing, viscosity passed through a minimum then sharply increased due to increasing amount of the crosslinking reaction. The temperature at minimum viscosity increased as the chain length became longer. After passing the minimum point, viscosity increased much faster for meta BMIs (3BE1, 3BE2) than para BMIs, however, the difference in the chain length did not show any appreciable difference in the viscosity increase rate (dη^∗/dT). Nonetheless, the final viscosity was lower for longer chains, because their crosslinking density would be lower.In isothermal curing, the final crosslinking density was expected to increase with temperature, which was shown via the increase in the final viscosity. The gelation time decreased with temperature, and the activation energy of the crosslinking reaction was obtained. Using the reaction kinetics parameters obtained from dynamic scanning calorimeter and Arrhenius type equation, the viscosity change during the isothermal curing was simulated and compared with the measurements.