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.     

Initial step of anthracene‐sensitized photoacid generation from diphenyliodonium hexafluorophosphate in an epoxy matrix studied by steady‐state and laser‐flash photolyses

The anthracene‐sensitized photodecomposition of diphenyliodonium hexafluorophosphate was studied in an epoxy matrix. From steady‐state photolysis, the generation of protons, which are considered to be the actual initiators of the polymerization of epoxides, was confirmed. In addition, 9‐phenylanthracene was detected as a main product from anthracene. From time‐resolved laser‐flash photolysis, a broad absorption band with a peak at about 500 nm was observed that was thought to be due to the precursor of 9‐phenylanthracene. On the basis of these results, we propose electron transfer from anthracene in the excited singlet state to the diphenyliodonium cation as the initial step of photoacid generation. This process is followed by fast chemical reactions, which generate 9‐phenylanthracene and protons, and back electron transfer from the diphenyliodine radical to the anthracene cation radical. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2937–2946, 2001     

Calorimetric study of the cubic mesogen, ACBC(6)

The heat capacity of the cubic mesogen ACBC(16) was measured between 16 and 500 K by adiabatic calorimetry. As well as the known condensed phases, a new crystalline phase was found to undergo a glass transition at around 165 K. Phase transitions between crystal, SmC, cubic, and isotropic liquid phases took place at 399.16, 431.15, and 474.30 K, respectively. As in the case of ANBC, a broad hump was observed in the heat capacity of the isotropic liquid phase. The first order nature of the SmC-cubic phase transition was confirmed for the first time by the observation of supercooling of the cubic phase. The broad hump in the isotropic liquid phase was shown to extend to a low temperature side if the isotropic liquid was supercooled, suggesting that the event occurring at the hump is not directly related to the cubic-isotropic liquid phase transition.     

Adiabatic calorimetry of the metallomesogen purple cobalt stearate Co(O2CC17H35)2

The heat capacity of the metallomesogen purple cobalt stearate Co(O₂CC₁₇H₃₅)₂ has been measured by adiabatic calorimetry at temperatures between 16 and 420 K. This compound exhibits two crystalline phases (low temperature Cr2 and high temperature Cr1 phases), mesophase (M phase), and isotropic liquid (I phase). A third crystalline phase Cr3, which is entirely metastable with respect to all the others, is suggested by DSC studies. The Cr2-to-Cr1, Cr1-to-M, and M-to-I phase transitions occurred at 362.1, 380.9, and 400.4 K, respectively. The enthalpy and entropy gains at these phase transitions were determined. The mesophase is either smectic A or nematic.     

Cyclic flow-injection analysis for the repetitive determination of zinc with 2-(5-bromo-2-pyridylazo)-5-[N-n-propyl-N-(3-sulfopropyl)amino]phenol and EDTA.

A circulatory flow-injection method (cyclic FIA) for the repetitive determination of zinc has been proposed. The procedure involves the use of 2-(5-bromo-2-pyridylazo)-5-[N-n-propyl-N-(3-sulfopropyl)amino]phenol (5-Br-PAPS) together with EDTA as a reagent carrier solution, which is recycled in a single-line flow system via a reservoir. The formed 5-Br-PAPS-Zn(II) complex was measured spectrophotometrically at 552 nm, and the signal intensity corresponded to the zinc concentration. After passing through a flow-through cell, the carrier stream then returned to the reservoir, and the main reagent, 5-Br-PAPS, was successfully regenerated by a ligand-exchange reaction with EDTA, allowing the repetitive determination of zinc. The calibration curve for zinc was linear in the concentration range from 0.4 to 10.0 mg dm(-3) with a correlation coefficient of 0.9995 (n = 6). The detection limit of this method was 0.02 mg dm(-3) (S/N= 3). This method allowed as many as 300 repetitive determinations of 2.0 mg dm(-3) zinc solution with only 100 cm3 of the circulating carrier solution, providing a reduction in the consumption of reagents and an elimination of waste, an important approach towards clean chemistry.     

Micro‐ and Nano‐Technologies for Lipid Bilayer‐Based Ion‐Channel Functional Assays

Ion channel proteins provide gated pores that allow ions to passively flow across cell membranes. Owing to their crucial roles in regulating transmembrane ion flow, ion channel proteins have attracted the attention of pharmaceutical investigators as drug targets for use in the studies of both therapeutics and side effects. In this review, we discuss the current technologies that are used in the formation of ion channel‐integrated bilayer lipid membranes (BLMs) in microfabricated devices as a potential platform for next‐generation drug screening systems. Advances in BLM fabrication methodology have allowed the preparation of BLMs in sophisticated formats, such as microfluidic, automated, and/or array systems, which can be combined with channel current recordings. A much more critical step is the integration of the target channels into BLMs. Current technologies for the functional reconstitution of ion channel proteins are presented and discussed. Finally, the remaining issues of the BLM‐based methods for recording ion channel activities and their potential applications as drug screening systems are discussed.     

Transformation of actoHMM assembly confined in cell-sized liposome

To construct a simple model of a cellular system equipped with motor proteins, cell-sized giant liposomes encapsulating various amounts of actoHMM, the complexes of actin filaments (F-actin) and heavy meromyosin (HMM, an actin-related molecular motor), with a depletion reagent to mimic the crowding effect of inside of living cell, were prepared. We adapted the methodology of the spontaneous transfer of water-in-oil (W/O) droplets through a phospholipid monolayer into the bulk aqueous phase and successfully prepared stable giant liposomes encapsulating the solution with a physiological salt concentration containing the desired concentrations of actoHMM, which had been almost impossible to obtain using currently adapted methodologies such as natural swelling and electro-formation on an electrode. We then examined the effect of ATP on the cytoskeleton components confined in those cell-sized liposomes, because ATP is known to drive the sliding motion for actoHMM. We added α-hemolysin, a bacterial membrane pore-forming toxin, to the bathing solution and obtained liposomes with the protein pores embedded on the bilayer membrane to allow the transfer of ATP inside the liposomes. We show that, by the ATP supply, the actoHMM bundles inside the liposomes exhibit specific changes in spatial distribution, caused by the active sliding between F-actin and HMM. Interestingly, all F-actins localized around the inner periphery of liposomes smaller than a critical size, whereas in the bulk solution and also in larger liposomes, the actin bundles formed aster-like structures under the same conditions.     

Selective catalysts for the production of nitrogen-containing compounds

Herewith are the two processes developed by Nitto, which produce N-containing compounds such as hydrogen cyanide and methylamines. These processes are characterized by unique selective catalysts: an Fe–Sb–O based fluid-bed catalyst for ammoxidation of methanol and a shape-selective zeolite catalyst for ammonolysis of methanol.     

A Coset-Type Construction for the Deformed Virasoro Algebra

An analog of the minimal unitary series representations for the deformed Virasoro algebra is constructed using vertex operators of the quantum affine algebra U_q(sl₂). A similar construction is proposed for the elliptic algebra A_q,p(sl₂).