Regiocontrolled copolymerization of methyl acrylate with carbon monoxide

An alternating copolymer of methyl acrylate with carbon monoxide has been synthesized for the first time via coordination polymerization using palladium complexes of phosphine-sulfonic acid as catalysts. The highly controlled head-to-tail structure of the copolymer was confirmed by NMR spectra. Subsequent insertion of carbon monoxide and methyl acrylate to methylpalladium species provided gamma-ketoalkylpalladium 2. The present system apparently conquered the difficulty in coordination-insertion of CO to 2.     

Electrochemical determination of the superoxide ion concentration from KO2 dissolved in dimethyl sulfoxide.

An electrochemical determination of the O2- concentration from KO2 in DMSO solution using steady state microelectrode voltammetry shows that the KO2/DMSO method with the combined use of a crown compound or sonication is a reliable and simple technique for introduction of O2- to the biomimitic reaction system.     

A density functional theory study of self-regenerating catalysts LaFe(1-x)M(x)O(3-y) (M = Pd, Rh, Pt)

Periodic density functional theory was used to investigate the stability and electronic structures of precious-metal atoms in the vicinity of LaFe(1-x)M(x)O(3) (M = Pd, Rh, Pt) perovskite catalyst surfaces. It was found that the surface segregation of Pd and Pt is significantly stabilized by the introduction of O vacancies, whereas the solid-solution phase is favorable for Rh, suggesting an important role of O vacancies in the self-regeneration of Pd and Pt. On the basis of the results, we propose a possible scenario for the self-regeneration of the precious metal in the perovskite catalyst.     

Pd-catalyzed copolymerization of methyl acrylate with carbon monoxide: structures, properties and mechanistic aspects toward ligand design

Full details are provided for the alternating copolymerization of acrylic esters with carbon monoxide (CO) catalyzed by palladium species bearing a phosphine-sulfonate bidentate ligand. The copolymer of methyl acrylate (MA) and CO had complete regioregularity with stereocenters that slowly epimerize in the presence of methanol. In the presence of ethylene, terpolymers of MA/ethylene/CO were also prepared. The glass transition temperatures of the co- and terpolymers were higher than that of the ethylene/CO copolymer. Both experimental and theoretical investigations were performed to clarify the superior nature of the palladium phosphine-sulfonate system compared to an unsuccessful conventional palladium diphosphine system: (i) The reversible insertion of CO was directly observed with the isolated alkylpalladium complexes, [{o-((o-MeOC(6)H(4))(2)P)C(6)H(4)SO(3)}PdCH(CO(2)Me)CH(2)COMe], whereas it was not observed with the corresponding complex bearing 1,2-bis(diphenylphosphino)ethane (DPPE). (ii) The transition state of the subsequent MA insertion, the rate-determining step of the catalytic cycle, was lower in energy in the phosphine-sulfonate system than in the DPPE system. This stabilization could be attributed to the less hindered sulfonate moiety as well as the stronger back-donation from palladium to the electron-deficient olefin, which is located trans to the sulfonate.     

Evaluation of electrodeposited gold nanostructures for applications in QCM sensing

The electrodeposition of gold nanostructures increases the surface area of a biosensor, which brings an enhancement of the sensitivity by increasing the amount of analyte binding to the surface. To evaluate the relationship among the surface structure, the area and the analyte binding, we quantitatively analyzed them for quartz crystal microbalance (QCM) sensing by scanning electron microscopy and cyclic voltammetry measurements. The results indicate a several-times increase of analyte bindings, and also the limitation of the sensing performance.     

Observation of band structure on amorphous silicon surface and performance of solar cells with controlled band offsets on hetero-junctions

Control of band offsets on hetero-junctions is important to achieve a higher efficiency amorphous silicon-based solar cell. It is expected to improve cell's properties of Voc and FF by suppressing band offsets on the junction. The configuration of conduction band level (Ec), valence band level (Ev) and Fermi level (Ef) based on vacuum level governs the formation of band offset on the junction. We show that the configuration of the band structure on the surface of amorphous Si thin film is deposited by plasma-CVD equipment with a VHF power supply. Ec and Ev were obtained from ionization energy and energy band gap observed by ultraviolet photoemission spectroscopy and optical measurement, respectively. Ef was measured as work function by means of Kelvin probe method. As a result, it is found that shifts of energy levels originate from change of bonding characteristics in the amorphous Si network. This phenomenon is peculiar to amorphous Si-based materials. The results indicate that the upper shift of Ec and Ev are effective in suppressing band offsets on the hetero-junction. We show the performance of solar cells with controlled band offsets on hetero-junctions and discuss the possibility of higher Voc and FF by employing amorphous Si-based materials.     

Open Algebraic Surfaces with Finite Group Actions

Suppose that a finite group G acts algebraically on a log projective surface (V, Delta) in such a way that Delta is G-stable. Suppose kappa(V - Delta) union SingV) = -infinity We first look for the conditions under which the Mori theory can be applied equivariantly and observe what we obtain from the Mori theory. We then consider the P¹-fibrations which are preserved by the actions of G.     

Simultaneous determination of charge number and diffusion coefficient of 2-chloro-1,4-dimethoxybenzene in acetonitrile using potential-step chronoamperometry

Potential-step chronoamperometry using a microdisk electrode was carried out for the simultaneous determination of the charge number and diffusion coefficients of natural electron-mediator dimethoxybenzene analogues during electro-oxidation. The process was verified as a one-electron oxidation during the radical cation formation.     

Effects of a central metal on the organization of 5,10,15,20-tetra-(p-chlorophenyl)-rare earth porphyrin hydroxyl compound at the air/water interface and in Langmuir-Blodgett films

Langmuir monolayers and Langmuir-Blodgett (LB) films of 5,10,15,20-tetra-(p-chlorophenyl) terbium/gadolinium porphyrin hydroxyl compound (TbOH and GdOH) and their mixtures with stearic acid (SA) in a molar ratio of 1:1 were investigated by Brewster angle microscopy (BAM), ultraviolet-visible (UV-vis), and infrared (IR) spectroscopy and atomic force microscopy (AFM). pi-A isotherms showed that well-defined Langmuir monolayers were formed at an air/water interface for the porphyrins and their mixture with SA. The BAM observations suggest that the pi-pi interaction between the GdOH molecules is stronger than that between the TbOH molecules. This result can be further confirmed by the AFM measurements. After the introduction of SA, the pi-pi interaction between the TbOH molecules is broken and thus two phases formed in the mixed LB film. However, it cannot break the stronger pi-pi interaction between the GdOH molecules. Therefore, no phase separation is observed in the GdOH/SA LB film. IR reflection-absorption (RA) spectra showed that the COOH groups of SA are partly converted to COO(-) groups, suggesting that there is an interaction between MOH and SA in the films. This interaction leads the benzene rings of TbOH to rotate toward parallel to the substrate and those of GdOH to rotate toward perpendicular to the substrate. All these results have demonstrated that the central metal ions have great effects on the organization and formation of the films.     

Bioactive saponins and glycosides. XXIII. Triterpene saponins with gastroprotective effect from the seeds of Camellia sinensis--theasaponins E3, E4, E5, E6, and E7

The saponin fraction from the seeds of the tea plant [Camellia sinensis (L.) O. KUNTZE (Theaceae)] was found to exhibit potent protective effects on ethanol- and indomethacin-induced gastric mucosal lesions in rats. Five new triterpene saponins, theasaponins E3 (1), E4 (2), E5 (3), E6 (4), and E7 (5), were isolated together with 11 known saponins from the saponin fraction. The chemical structures of 1-5 were elucidated on the basis of chemical and physicochemical evidence. Among the isolated saponins, theasaponins E1 (6), E2 (7), and E5 (3) and assamsaponin C (10) showed an inhibitory effect on ethanol-induced gastric mucosal lesions at a dose of 5.0 mg/kg, p.o. and their activities were stronger than that of omeplazole. With regard to the structure-activity relationships of theasaponins, the following structural requirements for a protective effect on ethanol-induced gastric lesions were suggested; 1) the 21- and/or 22-acyl groups are essential for the activity, 2) acetylation of the 16-hydroxyl group reduce the activity.