A study of the calcium complex of a glucosylceramide, soya-cerebroside II

In order to study calcium ion complex of soya-cerebroside II (1), an ionophoretic glucosylceramide isolated from soybean, C8-cerebroside (3) and 3,3',6'-trideoxy-C8-cerebroside (4) are designed and synthesized. On the basis of extensive 1H-NMR studies in the presence of Ca2+ and a continuous variation method via (1)H-NMR, soya-cerebroside II is suggested to form a calcium complex with 1/Ca2+ ratio of 1 : 1. Soya-cerebroside II serves as a tridentate chelating ligand for Ca2+; the amide carbonyl, C2'-hydroxy, and C2'-hydroxy oxygens are responsible for the Ca2+ binding. Soya-cerebroside II is structurally analogous to a neural glucosylceramide. Thus, the accumulated neural glucosylceramide inside of endoplasmic reticulum (ER) membrane may serve as an endogenous Ca2+-binding and -transport molecule (ionophore) that result in mobilization of Ca2+ from intracellular calcium stores.     

Ethylene adsorption on regularly stepped copper surface: C2H4 on Cu(210)

Ethylene adsorption on regularly stepped Cu(210) surface was investigated with infrared reflection–adsorption spectroscopy and temperature programmed desorption. At 90 K, π-bonded ethylene was adsorbed on Cu(210) molecularly and all species were desorbed below 160 K. There were three types of π-bonded ethylene on the surface. Recent experimental studies have suggested that ethylene is dehydrogenated on Cu(410) due to the regular step [Kravchuk et al., J. Phys. Chem. C, 113 (2009) 20881]. However, neither the formation of di-σ-bonded ethylene nor dehydrogenation occurred on Cu(210).     

Spin-dependent nuclear weak processes and nucleosynthesis in stars

Spin dependent nuclear weak processes and nucleosynthesis in stars are investigated based on recent advances in shell model studies of stable and unstable exotic nuclei. Three topics on (1) neutrino-nucleus reactions in supernova explosions and nucleosynthesis of light elements as well as Mn, (2) electron capture reaction rates on Ni and Co isotopes at high densities and temperatures in the core-collapse process, and (3) new β-decay half-lives of N=126 isotones obtained by including both the Gamow-Teller and the first-forbidden transitions, and the effects on the element abundance in the r-process at the third peak region (A∼195), are studied with the use of new shell model Hamiltonians.     

Oxidation of TiNi surface with hyperthermal oxygen molecular beams

We report results of our detailed studies on the initial oxidation process of TiNi with a 2 eV hyperthermal oxygen molecular beam (HOMB) and thermal O₂ in the backfilling. The oxidation processes are monitored by X-ray photoemission spectroscopy (XPS) measurements in conjunction with synchrotron radiation (SR). In the early stage of oxidation, the precursor mediated dissociative adsorption is the dominant reaction mechanism. In the oxide formation process at higher O coverage, HOMB has the advantage in the dissociation process of O₂ molecule and can grow TiO₂ layers with the underlying TiO_x-rich and/or Ni-rich layers. We succeeded in fabricating thick Ni-free TiO₂ layer, possibly blue colored rutile TiO₂, combining HOMB and surface annealing.     

Synthesis of endohedral metallofullerene glycoconjugates by carbene addition

Endohedral metallofullerene glycoconjugates were synthesized under mild conditions by carbene addition using appropriate glycosylidene-derived diazirine with La(2)@I(h)-C(80). NMR spectroscopic studies revealed that the glycoconjugate consists of two diastereomers of [6,6]-open mono-adducts. The electronic properties were characterized using Vis/NIR absorption spectroscopy and electrochemical measurements. This study demonstrates that glycosylidene carbene is useful to incorporate carbohydrate moieties onto endohedral metallofullerene surfaces.     

Reconstitution of bacterial photosynthetic unit in a lipid bilayer studied by single-molecule spectroscopy at 5 K

As a model of photosynthetic unit (PSU), self-assembled aggregates of pigment-protein complexes from photosynthetic bacteria were prepared in a lipid bilayer by reconstitution of the light-harvesting 2 (LH2) complex and light-harvesting 1-reaction center (LH1-RC) complex through detergent removal of their micelles in the presence of lipids. By performing polarization-controlled fluorescence and fluorescence-excitation spectroscopy on single aggregates at a temperature of 5 K, the composition of individual aggregates was determined and excitation energy transfer (EET) between constituent complexes was observed. LH2 and LH1-RC from a bacterium, Rhodobacter (Rb.) sphaeroides, were found to form a trimeric aggregate in which EET takes place from one LH2 to two LH1-RCs. In contrast, a heterodimer of LH2 and LH1-RC in which EET works was found to assemble from a combination of complexes of different bacterial species, that is, LH2 from Rb. sphaeroides and LH1-RC from Rhodopseudomonas (Rps.) palustris.     

Study of Trioxane Production Process with Super‐ or Subcritical Fluid as Solvent and Extractant

A super‐ or subcritical fluid was used as a reaction solvent for nonaqueous trioxane synthesis instead of common organic solvents. The generation of trioxane from paraformaldehyde was observed in the presence of the catalyst when carbon dioxide reached a supercritical region, suggesting that the supercritical carbon dioxide acted as the reaction solvent. In the case of Freon 12, the trioxane was effectively produced even in a subcritical state.     

Conformations of spermine in adenosine triphosphate complex: the structural basis for weak bimolecular interactions of major cellular electrolytes

Selectively (2)H- and (13)C-labeled spermines (SPM) were efficiently synthesized and analyzed by NMR spectroscopy to determine the spin-spin coupling constants for six conformationally relevant bonds. SPM that is composed of three alkyl moieties, a butanylene, and two propanylene chains undergoes a conformational change when interacting with multivalent anions (e.g., adenosine triphosphate (ATP), ATP-Mg(2+) , and tripolyphosphate). Upon interaction with ATP, the C-C bonds, which affect the distance between the neighboring pairs of ammonium groups (i.e., N1/N5 and N5/N5'), increase the population of gauche rotamers by 17-20% relative to those in the 4 HCl salt of SPM. However, the trend in increments of the gauche conformers for the SPM-ATP complex profoundly differs from that of the spermidine (SPD)-ATP complex. This implies that SPM may preferentially recognize the adenyl group of ATP rather than the tripolyphosphate moiety. This may account for the higher affinity of SPM to ATP-Mg(2+) than with that of SPD, which chiefly interacts with β- and γ-phosphates and is easily replaced by Mg(2+) . These results may provide a clue for the further understanding of the structural basis of polyamine biological functions.