Trans-Bilayer Ion Conduction by Proline Containing Cyclic Hexapeptides and Effects of Amino Acid Substitutions on Ion Conducting Properties

Several ion channel forming cyclic peptides have been reported over the past two decades and various ion conducting mechanisms have been proposed. In this article, we report on amino acid substitutions in cyclic hexapeptides and their effects on the ion conducting properties of these peptides. Cyclic hexapeptides, cyclo(Pro-Xxx-Yyy)2, containing two Pro residues, were used as the main framework. The substitution is performed at the Xxx positions with cationic/hydrophilic Lys or hydrophobic Leu. Yyy positions were substituted with D-Phe, D-Ala, or Gly. The peptides which were absent Lys residues showed ion conducting profiles with clear transitions of electric currents, whereas the peptides containing Lys residues tended to exhibit spiky or burst-like profiles. These profiles were altered single state profiles by the protection of ε-amino groups with aromatic protecting groups. The protected analogs exhibited significant decrease in ion conductance. These results indicated that peptides containing Lys conduct ions without forming ring stacked tube-like structure. Ion channel properties were also affected by conformational changes of the cyclic peptides induced by substitution of the Yyy positions. Enhancement of intramolecular β-turn structures of cyclic peptides tended to decrease their ion conductance values

High-pressure synthesis of new filled skutterudite compounds SrT4As12 (T = Fe, Ru, Os)

We have succeeded in synthesizing samples of new filled skutterudite compounds SrT 4As12 (T = Fe, Ru, and Os) using a high-pressure synthesis technique. These compounds have lattice constants of 8.351, 8.521, and 8.561 Å, respectively. The physical properties of the compounds are reported for the first time. The temperature dependences of the electrical resistivity for SrT 4As12 (T = Fe, Ru, and Os) exhibit metallic behaviors. The electrical resistivity and magnetic measurements indicates that SrOs4As12 is a new superconductor with a transition temperature of 4.8 K. A broad maximum of magnetic susceptibility at around 50 K and a large electronic specific heat coefficient of 58 mJ mol−1 K−2 suggest that SrFe4As12 is a nearly ferromagnetic metal with spin fluctuations of Fe 3d electrons

Superlattice formation lifting degeneracy protected by non-symmorphic symmetry through a metal-insulator transition in RuAs

The single crystal of RuAs obtained by Bi-flux method shows obvious successive metal-insulator transitions at T_MI1~255 K and T_MI2~195$ K. The X-ray diffraction measurement reveals a formation of superlattice of 3x3x3 of the original unit cell below T_MI2, accompanied by a change of the crystal system from the orthorhombic structure to the monoclinic one. Simple dimerization of the Ru ions is nor seen in the ground state. The multiple As sites observed in nuclear quadrupole resonance (NQR) spectrum also demonstrate the formation of the superlattice in the ground state, which is clarified to be nonmagnetic. The divergence in 1/T_1 at T_MI1 shows that a symmetry lowering by the metal-insulator transition is accompanied by strong critical fluctuations of some degrees of freedom. Using the structural parameters in the insulating state, the first principle calculation reproduces successfully the reasonable size of nuclear quadrupole frequencies for the multiple As sites, ensuring the high validity of the structural parameters. The calculation also gives a remarkable suppression in the density of states (DOS) near the Fermi level, although the gap opening is insufficient. A coupled modulation of the calculated Ru d electron numbers and the crystal structure proposes a formation of charge density wave (CDW) in RuAs. Some lacking factors remain, but it shows that a lifting of degeneracy protected by the non-symmorphic symmetry through the superlattice formation is a key ingredient for the metal-insulator transition in RuAs.Comment: 10 pages, 10 figure

High-pressure Synthesis and Bulk Modulus of Non-centrosymmetric Superconductor Mo3Al2C

Mo3Al2C is a superconductor without inversion symmetry (the transition temperature T C ~ 9K). We have succeeded in preparing high-quality samples of Mo3Al2C using the high-pressure synthesis technique. The samples were characterized by powder x-ray diffraction (XRD) analysis. Furthermore, powder XRD patterns for the samples with synchrotron radiation have been studied under high pressures up to around 10 GPa and the volume versus pressure curve for the compound has been investigated. A bulk modulus was estimated to be 221 GPa

The structural, transport, and magnetic properties of Yb-filled skutterudites YbyFexCo4−xSb12 synthesized under high pressure

The effects of Fe-substitution on partially Yb filled skutterudites YbyFexCo4-xSb12 are presented from the viewpoint of crystal structure and thermoelectric, magnetic, and transport properties. A series of polycrystalline n-type YbyFexCo4-xSb12 (0.21 ≤ y ≤ 0.47, 0 ≤ x ≤ 0.76) samples were prepared using a high-pressure and high-temperature method. X-ray diffraction data suggest that all the compounds are high-purity skutterudites. For the YbyFexCo4-xSb12 with Yb content higher than 0.29 and Fe content lower than 1, the lattice constant shows a saturated behavior despite the change in the Yb/Fe content. Rietveld refinement based on the synchrotron radiation X-ray data implies that the rectangular Sb4 ring is transformed into square with increasing Yb content and/or Fe substitution content. The Yb valence gradually decreases as the Fe content increases from magnetic susceptibility analysis. According to the specific heat analysis, higher Yb filling benefits the lower Debye temperature while the Fe substitution leads to an increased Debye temperature. The Einstein temperature decreased with increasing Yb filling fraction, but Fe substitution for the Co site does not change the Einstein temperature further. Fe-substitution causes the reduction of total thermal conductivity κ, which mainly originates from the decrease of electron thermal conductivity contribution. The resistivity, Seebeck coefficient, thermal conductivity, and figure of merit (ZT) were effectively tuned due to the optimization of the carrier concentration. At the same carrier concentration, the hall mobility was decreased by Fe substitution. The proper Fe substitution content (0.2 in Yb0.25Fe0.2Co3.8Sb12) can result in a relatively high effective mass

Suppression of ferromagnetic spin fluctuations in the filled skutterudite superconductor SrOs4As12 revealed by As-75 NMR-NQR measurements

Motivated by the recent observation of ferromagnetic spin correlations in the filled skutterudite SrFe4As12 [Q.-P. Ding et al., Phys. Rev. B 98, 155149 (2018)], we have carried out As-75 nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements to investigate the role of magnetic fluctuations in the newly discovered isostructural superconductor SrOs4As12 with a superconducting transition temperature of T-c similar to 4.8 K. Knight shift K determined by the NQR spectrum under a small magnetic field (<= 0.5 T) is nearly independent of temperature, consistent with the temperature dependence of the magnetic susceptibility. The nuclear spin-lattice relaxation rate divided by temperature, 1/T1T, is nearly independent of temperature above similar to 50 K and increases slightly with decreasing temperature below the temperature. The temperature dependence is reasonably explained by a simple model where a flat band structure with a small ledge near the Fermi energy is assumed. By comparing the present NMR data with those in SrFe4As12, we found that the values of vertical bar K vertical bar and 1/T1T in SrOs4As12 are smaller than those in SrFe4As12, indicating no obvious ferromagnetic spin correlations in SrOs4As12. From the temperature dependence of 1/T-1 in the superconducting state, an s-wave superconductivity is realized

Longevity-associated NADH Dehydrogenase Subunit-2 237 Leu/Met Polymorphism Modulates the Effects of Daily Alcohol Drinking on Yearly Changes in Serum Total and LDL Cholesterol in Japanese Men

Reduced nicotinamide adenine dinucleotide (NADH) dehydrogenase subunit 2 237 leucine/methionine (ND2-237 Leu/Met) polymorphism, is reportedly associated with longevity in the Japanese population. The ND2-237Met genotype may exert resistance to atherogenic diseases, such as myocardial infarction or cerebrovascular disorders. To investigate whether ND2-237 Leu/Met polymorphism is associated with yearly changes in serum lipid levels, we conducted a longitudinal study of 107 healthy Japanese male subjects. Analysis of covariance revealed that the interaction between the ND2-237 Leu/Met genotypes and habitual drinking was significantly associated with yearly changes in serum total cholesterol (TC) and low-density lipoprotein cholesterol (LDLC) levels (p0.036 and p0.006, respectively). In multiple regression analysis, daily drinking was significantly and positively associated with yearly changes in serum LDLC levels in men with ND2-237Met (p0.026). After adjusting for covariates, yearly changes in serum LDLC levels were significantly lower in non-daily drinkers with ND2-237Met than in those with ND2-237Leu (p0.047). These results suggest that ND2-237Met has a beneficial impact on yearly changes in serum LDLC in non-daily drinkers but not in daily drinkers.</p