Frequency dependence of electron spin-lattice relaxation rate at 5–450 MHz in pristine trans-polyacetylene --- new evidence of one dimensional diffusive motion of electron spin (neutral soliton) ---

Electron spin-lattice relaxation rate T_l^?1 has been measured at low frequencies 5–450 MHz in pristine trans-polyacetylene. Frequency dependence of T_l^?1 gave dimensionality of diffusive motion of electron spins (neutral soliton). Relaxation mechanism was identified as dipolar and hyperfine origin based on an electron spin concentration dependence of T_l^?1.     

A novel synthesis of benzo- and indolo[a]quinolizidines by intramolecular diels-alder reaction of l-azadienes

Intramolecular Diels-Alder reaction of l-azadienes was conducted by heating the α,β-unsaturated amides (2a ～ d and 6) in the presence of trimethyl- chlorosilane, triethylamine and zinc chloride to give benzo- and indolo[a]- quinolizidines (5a ～ e and 7).     

Alignment of iodine species in stretched polyacetylene films

The¹²⁹I Mössbauer spectroscopy has been applied to iodine-doped highly conducting polyacetylene. For the unstretched polyacetylene films, the iodine species of I^?, I ₃ ^? and I ₅ ^? are observed. The polyiodides have symmetrical charge population. In addition to these anions, a small amount of iodines is covalently bonding to the carbon atoms, breaking the double bonds of the main chain. For the stretched polyacetylene films, the measurements were done under the condition that the stretch direction was parallel or perpendicular to the direction of incident ψ-rays. The relative change of the intensities of the Mössbauer quadrupole-split lines reveals the alignment of the polyiodine anions in the stretched film.     

Kinetic and DFT studies on the Ag/TiO2-photocatalyzed selective reduction of nitrobenzene to aniline.

TiO2 particles loaded with silver nanoparticles with a mean diameter of 1.5 nm exhibit a high photocatalytic activity (84 % conversion after 1 h irradiation) for the reduction of nitrobenzene to aniline with 100 % selectivity in the presence of CH3OH (concentration=100 mM). High-resolution transmission electron microscopic studies of Pt-photodeposited Ag/TiO2 demonstrate that the Ag nanoparticles act as reduction sites in the photocatalytic reaction. Both spectroscopic measurements and density functional theory (DFT) calculations reveal that nitrobenzene is selectively adsorbed onto the Ag surfaces of Ag/TiO2 via partial electron transfer from Ag to nitrobenzene, whereas the interaction between aniline and Ag/TiO2 is weak. The kinetic analysis indicates that the recombination between the electrons flowing into the Ag nanoparticle and the holes left in the TiO2 valence band is significantly suppressed, particularly in the presence of CH3OH. The high activity and selectivity in the present Ag/TiO2-photocatalyzed reduction are rationalized in terms of the charge separation efficiency, the selective adsorption of the reactants on the catalyst surfaces, and the restriction of the product readsorption.     

Molecular dynamics simulation of clustered DNA damage sites containing 8-oxoguanine and abasic site

Clustered DNA damage sites induced by ionizing radiation have been suggested to have serious consequences to organisms, such as cancer, due to their reduced probability to be repaired by the enzymatic repair machinery of the cell. Although experimental results have revealed that clustered DNA damage sites effectively retard the efficient function of repair enzymes, it remains unclear as to what particular factors influence this retardation. In this study, approaches based on molecular dynamics (MD) simulation have been applied to examine conformational changes and energetic properties of DNA molecules containing clustered damage sites consisting of two lesioned sites, namely 7,8-dihydro-8-oxoguanine (8-oxoG) and apurinic/apyrimidinic (AP) site, located within a few base pairs of each other. After 1 ns of MD simulation, one of the six DNA molecules containing a clustered damage site develops specific characteristic features: sharp bending at the lesioned site and weakening or complete loss of electrostatic interaction energy between 8-oxoG and bases located on the complementary strand. From these results it is suggested that these changes would make it difficult for the repair enzyme to bind to the lesions within the clustered damage site and thereby result in a reduction of its repair capacity.     

Studies on the syntheses of hetrocyclic and natural compounds. part 948: A simple and convenient synthesis of yohimbane and alloyohimbane

A simple method for the stereoselective synthesis of yohimbane (7) and alloyohimbane (5) via the diazoketone (2) from the anhydride (8), a symmetrical starting material, was examined. The preparation of pentacyclic ring systems contained in yohimbine and reserpine would be possible for the synthesis of such alkaloids by this method.     

Enantiomerically pure 2-bromo-2'-diphenylphosphinyl-1,1'- binaphthyl as a monophosphorus template for electrophilic functionalization in chiral MOP-type ligand synthesis

[reaction: see text] Pd-catalyzed monophosphinylation of (R)-2-bromo-2'-iodo-1,1'-binaphthyl with Ph(2)P(O)H afforded (R)-2-bromo-2'-diphenylphosphinyl-1,1'-binaphthyl in good yield with excellent chemoselectivity and no observable racemization. Subsequent lithiation in the presence of excess thiosulfonate furnished an enantiomerically pure sulfenylation product, which was reduced to afford a chiral S-MOP ligand.     

Studies on the syntheses of heterocyclic compounds. Part CDXCVII. Total syntheses of (±)-cryptaustoline and (±)-thaliporphine by the benzyne reaction

The indisputable benzyne reaction of 1-(5-bromo-3,4-dimethoxybenzyl)-1,2,3,4-tetrahydro-7-hydroxy-6-metlioxy-2-methylisoquinoline (II) with sodium amide in liquid ammonia afforded the following compounds, (±)-cryptaustoline iodide (VI), (±)-thaliporphine (VIII), 1 -(3,4-dimeth-oxybenzyl)- (III), and 1 -(2-amino-4,5-dimethoxybenzyl)-l,2,3,4-tetrahydro-7-hydroxy-6-meth-oxy-2-methylisoquinoline (IV).