Catalytic activity and regeneration property of a Pd nanoparticle encapsulated in a hollow porous carbon sphere for aerobic alcohol oxidation

A core-shell composite consisting of a palladium (Pd) nanoparticle and a hollow carbon shell (Pd@hmC) was employed as a catalyst for aerobic oxidation of various alcohols. The core-shell structure was synthesized by consecutive coatings of Pd nanoparticles with siliceous and carbon layers followed by removal of the intermediate siliceous layer. Structural characterizations using TEM and N(2) adsorption-desorption measurements revealed that Pd@hmC thus-obtained was composed of a Pd nanoparticle core of 3-6 nm in diameter and a hollow carbon shell with well-developed mesopore (ca. 2.5 nm in diameter) and micropore (ca. 0.4-0.8 nm in diameter) systems. When compared to some Pd-supported carbons, Pd@hmC showed a high level of catalytic activity for oxidation of benzyl alcohol into benzaldehyde using atmospheric pressure of O(2) as an oxidant. The Pd@hmC composite also exhibited a high level of catalytic activity for aerobic oxidations of other primary benzylic and allylic alcohols into corresponding aldehydes. The presence of a well-developed pore system in the lateral carbon shell enabled efficient diffusion of both substrates and products to reach the central Pd nanoparticles, leading to such high catalytic activities. This core-shell structure also provided high thermal stability of Pd nanoparticles toward coalescence and/or aggregation due to the physical isolation of each Pd nanoparticle from neighboring particles by the carbon shell: this specific property of Pd@hmC resulted in possible regeneration of catalytic activity for these aerobic oxidations by a high-temperature heat treatment of the sample recovered after catalytic reactions.     

Ionic liquid salt bridge based on tributyl(2-methoxyethyl)phosphonium bis(pentafluoroethanesulfonyl)amide for stable liquid junction potentials in highly diluted aqueous electrolyte solutions

A moderately hydrophobic ionic liquid, tributyl(2-methoxyethyl)phosphonium bis(pentafluoroethanesulfonyl)amide ([TBMOEP⁺][C₂C₂N⁻]), shows a very stable liquid junction potential upon contact with an aqueous solution whose ionic strength is as low as 1 μmol dm⁻³. The stability with the maximum excursion of the potential within ±0.5 mV for 30 min is very promising for accurate determination of pH and other single ion activities potentiometrically.     

Generation and development of RNA ligase ribozymes with modular architecture through "design and selection"

In vitro selection with long random RNA libraries has been used as a powerful method to generate novel functional RNAs, although it often requires laborious structural analysis of isolated RNA molecules. Rational RNA design is an attractive alternative to avoid this laborious step, but rational design of catalytic modules is still a challenging task. A hybrid strategy of in vitro selection and rational design has been proposed. With this strategy termed "design and selection," new ribozymes can be generated through installation of catalytic modules onto RNA scaffolds with defined 3D structures. This approach, the concept of which was inspired by the modular architecture of naturally occurring ribozymes, allows prediction of the overall architectures of the resulting ribozymes, and the structural modularity of the resulting ribozymes allows modification of their structures and functions. In this review, we summarize the design, generation, properties, and engineering of four classes of ligase ribozyme generated by design and selection.     

Test compounds for detecting the silanol effect on the elution of ionized amines in reversed‐phase LC

The effectiveness of several basic compounds for testing silica‐based stationary phases was reviewed by applying them to recent columns for reversed‐phase HPLC. Most octadecylsilylated (C18) stationary phases, prepared as a base‐deactivated material from high‐purity silica gel with endcapping, provided excellent peak shape and column efficiency for the bases including benzylamine and amitriptyline that once caused problems and were subsequently employed for testing silanol activities. However, a cyclic tertiary amine, dextrometorphan, was eluted as an acceptable peak from only a few columns at neutral pH. Such a more sensitive probe is expected to contribute to further improvement of the stationary phase for reversed‐phase HPLC.     

Mechanism of the decrease in catalytic activity of human cytochrome P450 2C9 polymorphic variants investigated by computational analysis

Cytochrome P450 (CYP) is deeply involved in the metabolism of chemicals including pharmaceuticals. Therefore, polymorphisms of this enzyme have been widely studied to avoid unfavorable side effects of drugs in chemotherapy. In this work, we performed computational analysis of the mechanism of the decrease in enzymatic activity for three typical polymorphisms in CYP 2C9 species: *2, *3, and *5. Based on the equilibrated structure obtained by molecular dynamics simulation, the volume of the binding pocket and the fluctuation of amino residues responsible for substrate holding were compared between the wild type and the three variants. Further docking simulation was carried out to evaluate the appropriateness of the binding pocket to accommodate substrate chemicals. Every polymorphic variant was suggested to be inferior to the wild type in enzymatic ability from the structural viewpoint. F‐G helices were obviously displaced outward in CYP2C9*2. Expansion of the binding pocket, especially the space near F′ helix, was remarkable in CYP2C9*3. Disappearance of the hydrogen bond between K helix and β4 loop was observed in CYP2C9*5. The reduction of catalytic activity of those variants can be explained from the deformation of the binding pocket and the consequent change in binding mode of substrate chemicals. The computational approach is effective for predicting the enzymatic activity of polymorphic variants of CYP. This prediction will be helpful for advanced drug design because calculations forecast unexpected change in drug efficacy for individuals. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

The effect of silica–alumina catalysts on degradation of polyolefins by a continuous flow reactor

Catalytic degradation of polyolefins was performed in a continuous flow reactor that allows the study of the degradation processes at steady state, characterized by constant values of reaction parameters and properties of the products. The continuous flow reactor was operated at atmospheric pressure and at feed rate of 0–1.5 kg h^?1 polyolefins over two silica–alumina catalysts having different SiO₂/Al₂O₃ mole ratio. Polyethylene (PE), polypropylene (PP) and polystyrene (PS) were degraded at 420, 380 and 360 °C respectively. The cracking effect of silica–alumina was proved by the increased amount of gaseous products and by the decreased molecular weight of liquid products. The differences in surface area and in concentration and acidic strength of active centers of the two catalysts affected the distribution of degradation products. Molar rate of degradation was increased in the presence of catalysts, however the mass rate of degradation was decreased leading to higher values of the calculated activation energies. These interesting results might open new perspectives in understanding the macroscopic mechanism for catalytic degradation of polyolefins.     

Medicinal Flowers. XXXI. Acylated oleanane-type triterpene saponins, Sasanquasaponins I-V, with antiallergic activity from the flower buds of Camellia sasanqua

The methanolic extract and its 1-butanol-soluble fraction from the flower buds of Camellia sasanqua THUNB. were found to show inhibitory activities on the release of β-hexosaminidase from rat basophile leukemia (RBL-2H3) cells. From the 1-butanol-soluble fraction, five new acylated oleanane-type triterpene saponins, sasanquasaponins I-V, were isolated together with a known saponin and their chemical structures were elucidated on the basis of chemical and physicochemical evidence. The principal saponin constituents, sasanquasaponins I-III, with an acyl group at the 22-position of the aglycon part showed the inhibitory effects on the release of β-hexosaminidase and some structure-activity relationships were reported.     

Quantum coherence in a superfluid Josephson junction

We report a new kind of experiment in which we take an array of nanoscale apertures that form a superfluid (4)He Josephson junction and apply quantum phase gradients directly along the array. We observe collective coherent behaviors from aperture elements, leading to quantum interference. Connections to superconducting and Bose-Einstein condensate Josephson junctions as well as phase coherence among the superfluid aperture array are discussed.     

Quantum interference of Rashba-type spin-split surface state electrons

We studied the quantum interference of electrons in the Bi (p(x), p(y)) orbital-derived j = 1/2 spin-split surface states at Bi/Ag(111)√3 × √3 surfaces of 10 monolayer thick Ag(111) films on Si(111) substrates. Surface electron standing waves were observed clearly at the energy (E) below the intersection of the two spin-split downward dispersing parabola bands (E(x)). The E dependence of the standing wave pattern reveals the dispersion as the average of the two spin-split surface bands due to the interference between |(k + Δ), ↑> and |-(k - Δ), ↑> [or (|(k - Δ), ↓>) and |-(k + Δ), ↓>] states. In contrast, it was impossible to deduce the dispersion from the standing wave pattern at E ≥ E(x) because the surface electron cannot find its backscattered state with the same spin polarization.     

Measurement of angular distribution of soft X‐ray radiation from thin targets in the tabletop storage ring MIRRORCLE‐20SX

The only available tabletop electron storage rings are the machines from the MIRRORCLE series. The electrons are accelerated in a microtron and injected into the storage ring. During its circulation, each electron passes through a tiny target many times, emitting a photon beam. Both the spectrum and the angular distribution of the radiation depend on the material, the thickness and the shape of the target. In this paper measured angular distributions of the radiation from several different targets in the magnetic field of the 20 MeV storage ring MIRRORCLE‐20SX are presented. The detector comprises a 3 mm × 3 mm × 8.5 µm plastic scintillator (PS) coupled to a photomultiplier by a bundle of optical fibers. The output of the photomultiplier is digitized by an IF converter. This detector is sensitive mostly to soft X‐ray radiation, and its PS is moved by a mechanical system in a plane perpendicular to the radiation axis. The measured angular distributions for Mo and Sn targets contain an annulus which is attributed to transition radiation. The angular distributions for Al, carbon nanotube and diamond‐like carbon (DLC) targets show some suppression of the radiation along the magnetic field. This is the first evidence of observation of the angular distribution of synchrotron Cherenkov radiation, which represents Cherenkov radiation in a magnetic field. The power radiated from the DLC target is estimated.