Extensive first-principles molecular dynamics study on Li encapsulation into C60 and its experimental confirmation.

The aim of increasing the production ratio of endohedral C60 by impinging foreign atoms against C60 is a crucial matter of the science and technology employed towards industrialization of these functional building block materials. Among these endohedral fullerenes, Li+@C60 exhibits a wide variety of physical and chemical phenomena and has the potential to be applicable in areas spanning the medical field to photovoltaics. However, currently, Li+@C60 can be experimentally produced with only ∼1% ratio using the plasma shower method with a 30 eV kinetic energy provided to the impinging Li+ ion. From extensive first-principles molecular dynamics simulations, it is found that the maximum production ratio of Li+@C60 per hit is increased to about 5.1% (5.3%) when a Li+ ion impinges vertically on a six-membered ring of C60 with 30 eV (40 eV) kinetic energy, although many C60 molecules are damaged during this collision. On the contrary, when it impinges vertically on a six-membered ring with 10 eV kinetic energy, the production ratio remains at 1.3%, but the C60 molecules are not damaged at all. On the other hand, when the C60 is randomly oriented, the production ratio reduces to about 3.7 ± 0.5%, 3.3 ± 0.5%, and 0.2 ± 0.03% for 30 eV, 40 eV, and 10 eV kinetic energy, respectively. Based on these observations we demonstrate the possibility of increasing the production ratio by fixing six-membered rings atop C60 using the Cu(111) substrate or UV light irradiation. In order to assess the ideal experimental production ratio, the 7Li solid NMR spectroscopy measurement is also performed for the multilayer randomly oriented C60 sample irradiated by Li+ using the plasma shower method combined with inductively coupled plasma atomic emission spectroscopy (ICP-AES). Time-of-flight mass spectroscopy measurements are also performed to cross check whether Li+@C60 molecules are produced in the sample. The resulting experimental estimate, 4% for 30 eV incident kinetic energy, fully agrees with our simulation results mentioned above, suggesting the consistency and accuracy of our simulations and experiments.

Pro-apoptotic activity of inhibitory PAS domain protein (IPAS), a negative regulator of HIF-1, through binding to pro-survival Bcl-2 family proteins.

Inhibitory PAS (Per/Arnt/Sim) domain protein (IPAS) is a dominant negative transcription factor that represses hypoxia-inducible factor 1 (HIF-1) activity. In this study, we show that IPAS also functions as a pro-apoptotic protein through binding to pro-survival Bcl-2 family members. In a previous paper, we reported that NF-κB-dependent IPAS induction by cobalt chloride repressed the hypoxic response in PC12 cells. We found that prolonged incubation under the same conditions caused apoptosis in PC12 cells. Repression of IPAS induction protected cells from apoptosis. Furthermore, knockdown of IPAS recovered cell viability. EGFP-IPAS protein was localized in both the nucleus and the cytoplasm, with a large fraction associated with mitochondria. Mitochondrial IPAS induced mitochondria depolarization and caspase-3 activation. Immunoprecipitation assays revealed that IPAS is associated with Bcl-x(L), Bcl-w and Mcl-1. The association of IPAS with Bcl-x(L) was also observed in living cells by the FLIM-based FRET analysis, indicating direct binding between the two proteins. IPAS contributed to dysfunction of Bcl-x(L) by inhibiting the interaction of Bcl-x(L) with Bax. These results demonstrate that IPAS functions as a dual function protein involved in transcription repression and apoptosis.

Spin-phonon coupling in multiferroic YbMnO(3) studied by Raman scattering.

Hexagonal YbMnO(3) bulk polycrystals were prepared and studied by Raman scattering in the temperature range of 15-300 K. A total of 15 phonon modes of A(1), E(1) and E(2) type were identified. Some E(2) phonon modes showed anomalous temperature variations in frequency at T(N)∼80 K, suggesting a coupling between the spin and phonon systems below T(N). As another evidence of spin-phonon coupling, softening of an A(1)-phonon mode for the O-Mn vibration was observed at ∼T(N). Substitution of Mn by Al suggests this view.

Raman scattering study of multiferroic Ho(3)Fe(5)O(12) thin films.

Ho(3)Fe(5)O(12) crystallizes in a body-centered cubic lattice and shows no ferroelectricity because of its highly symmetric (centrosymmetric) crystal structure. However, in heteroepitaxially grown thin films, Ho(3)Fe(5)O(12) may exhibit ferroelectricity because of lattice strains induced by the substrate. In this work, heteroepitaxial films of Ho(3)Fe(5)O(12) were grown with different thicknesses of 50-160 nm and studied by x-ray diffraction and Raman scattering. The results were compared with those of bulk polycrystals to characterize residual strains. At room temperature, Raman spectra of films revealed a phonon frequency shift from those of bulk samples, showing lattice distortion. There was a difference in the lattice distortion scheme between the thinner and thicker films. Results of x-ray diffraction were well correlated with the Raman data. Raman measurements at 300-800 K showed the existence of lattice strain up to ∼650 K. This suggests a remanent-polarization character of Ho(3)Fe(5)O(12) films up to this temperature. Closeness between the magnetic ordering temperature T(N) = 567 K and T(C)∼650 K may bring us the ideal multiferroic material with an enhanced magnetoelectric effect at room temperature.

Observation of phonons in multiferroic BiFeO(3) single crystals by Raman scattering.

We have grown BiFeO(3) bulk single crystals by a flux method and characterized the phonon spectra in detail by Raman scattering in the temperature range 4-1100 K. All the 13 Raman-active phonon modes predicted by group theory, 4A(1)+9E, were observed at low temperature and successfully assigned by a polarized Raman measurement. Moreover, drastic spectral changes in the Raman spectra were observed at temperatures 600-700 K and 1000-1100 K. These features are discussed from the viewpoint of phonon coupling with the magnetic ordering and the structural phase transition, respectively.

Raman scattering studies on multiferroic YMnO(3).

YMnO(3) is a multiferroic material in which ferroelectric and antiferromagnetic ordering can coexist. We have studied a YMnO(3) bulk crystal in detail by Raman scattering in a wide temperature range of 15-1200 K, with comparison to a previous experiment at room temperature and a theoretical prediction for Raman-active phonon modes. In the low-temperature ferroelectric phase, the observed phonon spectra showed anomalous temperature variation at the Néel temperature, T(N)∼80 K, suggesting a coupling between the spin and phonon systems below T(N). Furthermore, spectra for the high-temperature paraelectric phase, reported here for the first time, showed a sudden change at the Curie temperature T(C)>900 K, suggesting an abrupt structural phase change from the ferroelectric to the paraelectric phase.

Nanometer-nanosecond oscillatory expansion and contraction behavior of polymer films induced by 248 nm excimer laser excitation.

Microregional mechanical measurements of a poly[methylmethacrylate) film can be made by a combined probe/measurement laser system, as represented in the picture. The localized nature of the laser systems allow quantification of the degree of expansion and contraction processes, as well as the glass-rubber transition. Such nondestructive techniques lead to the elucidation of polymer morphological dynamics.

In vivo thrombus formation induced by complement activation on polymer surfaces.

To clarify involvement of complement activation in thrombus formation on polymer surfaces, in vitro complement activation was evaluated for polyethylene (PE) tubes radiation-graft copolymerized with acrylamide (AAm), acrylic acid (AC), 2-hydroxyethyl methacrylate (HEMA), N-vinylpyrrolidone (NVP), and vinyl alcohol (VOH), and compared to their in vivo antithrombogenicity and cell adherence in canine peripheral veins. The complement-activating surfaces (NVP and VOH) cause preferential adhesion of leukocytes and were more thrombogenic than the low complement-activating surfaces (AAm, PE, and HEMA). Infusion of naja haje cobra venom factor depressed leukocyte adhesion, followed by a marked decrease in thrombogenesis, for the strong classical-pathway-activating surface (NVP). Although estimation of in vitro activation for AC was inconclusive because of a large effect of adsorption, AC behaved like VOH in vivo. These results suggest that C5a(des Arg) mediated activation of leukocytes may play a role in thrombus formation by complement activation on polymer surfaces.

Morphological change and Raman spectrum of rabbit lens irradiated with ultraviolet laser beam.

The effect of ultraviolet rays on eyes was studied. An ultraviolet laser beam (XeCl 308 nm) was irradiated to rabbit eyes to investigate morphological changes of the lens fibers and molecular structural changes of the lens proteins at immediately, 15 days and 32 days after irradiation. 1. Scanning electron microscopic findings of the lens The lens fibers in the control eye were regularly and densely arranged in neat layers of hexahedrons. In the irradiated eye, the fibers at areas that seemed injured were disrupted and the disrupted ends were spherical-shaped. 2. Raman spectra of the lens 1) The relative intensity ratio (I825/I850) of the Raman scattering for the tyrosine residue and the relative intensity ratio (I3390/I2960) of the OH stretching mode (3390 cm-1) of water contained in the lens cortex showed slight changes in the irradiated eye compared to the control eye. 2) The relative intensity ratio (I2572/I2721) of the SH stretching mode (2572 cm-1) for the cysteine residue was 1.05 in the irradiated eye at 32 days after irradiation. It was lower than that in the control eye (1.22 +/- 0.08). This suggested the synthesis of S-S binding by oxidization.

Complement-induced thrombus formation on the surface of poly(N-vinylpyrrolidone)-grafted polyethylene.

The role of complement activation in thrombogenesis was investigated on the surface of hydrophilic monomer-graft copolymerized polyethylene (PE) tubes. N-vinylpyrrolidone (NVP)-grafted tubes activated in an in vitro complement system of canine serum; but no activation occurred in 2-hydroxyethyl methacrylate (HEMA)-grafted tubes. The relative patent time for NVP-grafted tubes implanted in canine peripheral veins was shorter than that for HEMA-grafted tubes and adhesion of numerous leucocytes was observed on the luminal surfaces of the NVP-grafted tubes. Decomplementation by prior administration of cobra venom factor elongated the relative patent time for NVP-grafted tubes only and also inhibited the adhesion of leucocytes onto them. These results suggest that the complement activation participates in thrombus formation on the polymer surfaces in canine veins.

Three new lanostanoids from Ganoderma lucidum.

Three new lanostanoids--ganodermenonol (1), ganodermadiol (2), and ganodermatriol (3) [isolated as its triacetate derivative (3a)]--were isolated from the MeOH extract of Ganoderma lucidum, together with ergosterol and its peroxide. The new compounds were identified as 26-hydroxy-5 alpha-lanosta-7,9(11),24-trien-3-one (1), 5 alpha-lanosta-7,9(11),24-triene-3 beta, 26-diol (2), and 5 alpha-lanosta-7,9(11),24-triene-3 beta, 26,27-triol (3) by their respective spectral data.