Antioxidant effects of photodegradation product of nifedipine

Recently, increasing evidence suggests that the antihypertensive drug nifedipine acts as a protective agent for endothelial cells, and that the activity is unrelated to its calcium channel blocking. Nifedipine is unstable under light and reportedly decomposes to a stable nitrosonifedipine (NO-NIF). NO-NIF has no antihypertensive effect, and it has been recognized as a contaminant of nifedipine. The present study for the first time demonstrated that NO-NIF changed to a NO-NIF radical in a time-dependent manner when it interacted with human umbilical vein endothelial cells (HUVECs). The electron paramagnetic resonance (EPR) signal of NO-NIF radicals in HUVECs showed an asymmetric pattern suggesting that the radicals were located in the membrane. The NO-NIF radicals had radical scavenging activity for 1,1-diphenyl-2-picrylhydrazyl, whereas neither NO-NIF nor nifedipine did. In addition, the NO-NIF radical more effectively quenched lipid peroxides than NO-NIF or nifedipine. Furthermore, NO-NIF attenuated the superoxide-derived free radicals in HUVECs stimulated with LY83583, and suppressed iron-nitrilotriacetic acid (Fe-NTA)-induced cytotoxicity in rat pheochromocytoma (PC12) cells. Our findings suggest that NO-NIF is a candidate for a new class of antioxidative drugs that protect cells against oxidative stress.     

Mass-analyzed velocity map imaging of doubly charged photofragments from C70

The velocity distributions of the fragments produced by dissociative photoionization of C(70) have been measured at several photon energies in the extreme UV region, by using a flight-time resolved velocity map imaging (VMI) technique combined with a high-temperature molecular beam and synchrotron radiation. Average kinetic energy release was estimated for the six reaction steps of consecutive C(2) emission, starting from C(70)(2+) → C(68)(2+) + C(2) to C(60)(2+)→ C(58)(2+) + C(2). The total kinetic energy generated in each step shows a general tendency to increase with increasing hν, except for the first and fifth steps. This propensity reflects statistical redistributions of the excess energy in the transition states for the above fragmentation mechanism. Analysis based on the finite-heat-bath theory predicts the detectable minimum cluster sizes at the end of the C(2)-emission decay chain. They accord well with the minimum sizes of the observed ions, if the excess energy in the primary C(70)(2+) is assumed to be smaller by ~15 eV than the maximum available energy. The present VMI experiments reveal remarkably small kinetic energy release in the fifth step, in contradiction to theoretical predictions, which suggests involvement of other fragmentation mechanisms in the formation of C(60)(2+).     

The orbital characters and kz dispersions of bands in iron-pnictide NaFeAs

The electronic structure and orbital characters of iron-pnictide NaFeAs have been studied by polarization dependent angle-resolved photoemission spectroscopy. Some of the bands are mixed with the orbitals of opposite symmetries, which could be interpreted by the hybridization among the bands. According to the photon energy dependent experiment, the k_z dispersions of the bands that cross the Fermi energy are weak in both paramagnetic and spin density wave states. However, a band well below the Fermi level shows a k_z dispersion of 41 meV, which mainly contains the d_z² orbital.     

Orbital density reconstruction for molecules

The experimental imaging of electronic orbitals has allowed one to gain a fascinating picture of quantum effects. We here show that the energetically high-lying orbitals that are accessible to experimental visualization in general differ, depending on which approach is used to calculate the orbitals. Therefore, orbital imaging faces the fundamental question of which orbitals are the ones that are visualized. Combining angular-resolved photoemission experiments with first-principles calculations, we show that the orbitals from self-interaction-free Kohn-Sham density functional theory are the ones best suited for the orbital-based interpretation of photoemission.     

Optical response of relativistic electrons in the polar BiTeI semiconductor

The transitions between the spin-split bands by spin-orbit interaction are relevant to many novel phenomena such as the resonant dynamical magnetoelectric effect and the spin Hall effect. We perform optical spectroscopy measurements combined with first-principles calculations to study these transitions in the recently discovered giant bulk Rashba spin-splitting system BiTeI. Several novel features are observed in the optical spectra of the material including a sharp edge singularity due to the reduced dimensionality of the joint density of states and a systematic doping dependence of the intraband transitions between the Rashba-split branches. These confirm the bulk nature of the Rashba-type splitting in BiTeI and manifest the relativistic nature of the electron dynamics in a solid.     

Anode Catalysts for Direct Hydrazine Fuel Cells: From Laboratory Test to an Electric Vehicle

Novel highly active electrocatalysts for hydrazine hydrate fuel cell application were developed, synthesized and integrated into an operation vehicle prototype. The materials show in both rotating disc electrode (RDE) and membrane electrode assembly (MEA) tests the world highest activity with peak current density of 16 000 A g^?1 (RDE) and 450 mW cm^?2 operated in air (MEA).     

Synthesis and self-association properties of diethynylbenzene macrocycles

We synthesized diethynylbenzene macrocycles (DBMs), cyclic oligomers of diethynylbenzene, having functional groups in the periphery of the macrocyclic framework and investigated their self-association properties in solution resulting from π-π stacking interaction. The tetrakis-DBM having hexadecyl ester groups showed dimerization behavior not only in chloroform-d, but also in o-dichlorobenzene-d₄.     

Quantum as a heat engine—the physics of intensities unique to the origins of life

Experimental endeavor for addressing the origins of life when viewed from the physical perspective presents a new opportunity of developing physics further for its own sake. A case in point is the issue of intensities. The physics of the origins of life may more readily be approachable by way of the dynamics of intensities or intensive quantities such as temperature and force strengths, compared to the standard dynamics of extensive quantities such as molecule numbers, densities, masses and charges. What is unique to the dynamics of intensities is that it is already contextual in addressing the context under which the intensities in focus are generated and maintained. In particular, because of the contextual nature of temperature grounded upon the material context in which the contextual elements move almost randomly with each other, the occurrence of temperature gradients provides an impetus for transforming the material context. The physical origins of life are just associated with the emergence of the robust material context that can serve as a heat engine. One likely candidate for the material context serving as a heat engine that could emerge in the presence of temperature gradients near hot vents in the primitive ocean on the Earth might have been a citric acid cycle running with no help of enzymes of biological origin. Underlying the emergence of a robust heat engine is the pruning principle of the faster temperature drop going with the greater stored latent heat applied to any reacting molecules crossing the temperature gradients.     

Enantiomer-selective membrane electrode for amino acid methyl esters

Polymeric membrane electrodes based on the chiral crown ether, 2,3:4,5-bis-[1,2-(3-phenylnaphtho)]-1,6,9,12,15,18-hexaoxacycloeicosa-2,4-diene, were prepared, and their characteristics were examined. The electrodes showed good enantiomer-selectivity for many amino acid methylesters, the enantiomer-selective factor reaching the high value of 13 for phenylglycine methyl ester. The electrodes responded preferably to the enantiomer forming the more stable complex with the crown ether. The electrodes proved useful for determining the concentrations of each enantiomer. The calculated concentrations from the potential changes of the electrodes were in good agreement with the predicted ones.