New approach to oligotriazoles using a cobalt complex of propargyl azides as a synthetic component

We have developed an efficient method for preparation of triazolamers using a dicobalt hexacarbonyl complex of propargyl azides (CPA) as a synthetic component. Several types of CPAs possessing the side chains found in the natural amino acids were prepared by Nicholas reaction as well as by a reaction of propargyl azides with dicobalt octacarbonyl. Triazolamers with both amino and carboxyl termini were readily synthesized by repetitive reaction sequence involving a copper-catalyzed 1,3-dipolar cycloaddition followed by an oxidative deprotection.     

From metal-organic framework to nanoporous carbon: toward a very high surface area and hydrogen uptake

In this work, with a zeolite-type metal-organic framework as both a precursor and a template and furfuryl alcohol as a second precursor, nanoporous carbon material has been prepared with an unexpectedly high surface area (3405 m(2)/g, BET method) and considerable hydrogen storage capacity (2.77 wt % at 77 K and 1 atm) as well as good electrochemical properties as an electrode material for electric double layer capacitors. The pore structure and surface area of the resultant carbon materials can be tuned simply by changing the calcination temperature.     

Near-infrared intersubband absorption in (CdS/ZnSe)/BeTe type-II super-lattices grown on GaAs substrate by MBE

We study the dependence of absorption wavelength on the well width in the (CdS/ZnSe)/BeTe super-lattices(SL). With well-width reduction, the wavelength decreases from 1.795 to 1.57 μm. Structural properties, strain state and interface composition are determined via XRD measurement. A (CdS/ZnSe)/Be_xMg_1−xTe structure is prepared and XRD reveals the average lattice constant match to GaAs substrate. TEM reveals that numerous stacking faults exist in the (CdS/ZnSe)/BeTe structure, and stacking faults are completely suppressed in (CdS/ZnSe)/Be_xMg_1−xTe SLs. Intersubband transition down to 1.535–1.55 μm have been observed in SLs.     

Reaction of alkynyltrimethylsilanes with a hypervalent organoiodine compound: A new general synthesis of alkynyliodonium salts

New general methods for the synthesis of alkynyl(phenyl)iodonium tetrafluoroborate 2 from alkynyltrimethylsilanes 1 utilizing the combination of iodosylbenzene and triethyloxonium tetrafluoroborate or boron trifluoride etherate were developed. The medium effect observed in the reaction was also discussed.     

Chemoenzymatic synthesis of naturally occurring benzyl 6-O-glycosyl-beta-D-glucopyranosides

Direct beta-glucosidation between benzyl alcohol and D-glucose (5) using the immobilized beta-glucosidase from almonds with the synthetic prepolymer ENTP-4000 gave a benzyl beta-D-glucoside (1) in 53% yield. The coupling of the benzyl beta-D-glucopyranoside congener (8) derived from 1 with phenyl 2,3,4-tri-O-acetyl-1-thio-beta-D-xylopyranoside (9), ethyl 2,3,4-tri-O-acetyl-1-thio-alpha-L-rhamnopyranoside (13), and 2,3,4-tri-O-acetyl-alpha-L-arabinopyranosyl bromide (15) afforded 10, 14, and 16, respectively, as coupled products. Deprotection of 10, 14, and 16 provided the synthetic benzyl beta-D-xylopyranosyl-(1-->6)-beta-D-glucopyranoside (2), benzyl alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranoside (3), and benzyl alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranoside (4), respectively.     

Electrochemical properties of core-shell TiC-TiO2 nanoparticle films immobilized at ITO electrode surfaces

Titanium carbide (TiC) nanoparticles are readily deposited onto tin-doped indium oxide (ITO) electrodes in the form of thin porous films. The nanoparticle deposits are electrically highly conducting and electrochemically active. In aqueous media (at pH 7) and at applied potentials positive of 0.3 V vs. SCE partial anodic surface oxidation and formation (at least in part) of novel core-shell TiC-TiO2 nanoparticles is observed. Significant thermal oxidation of TiC nanoparticles by heating in air occurs at a temperature of 250 degrees C and leads first to core-shell TiC-TiO2 nanoparticles, next at ca. 350 degrees C to TiO2 (anatase), and finally at temperatures higher than 750 degrees C to TiO2 (rutile). Electrochemically and thermally partially oxidized TiC nanoparticles still remain very active and for some redox systems electrocatalytically active. Scanning and transmission electron microscopy (SEM and TEM), temperature dependent XRD, quartz crystal microbalance, and voltammetric measurements are reported. The electrocatalytic properties of the core-shell TiC-TiO2 nanoparticulate films are surveyed for the oxidation of hydroquinone, ascorbic acid, and dopamine in aqueous buffer media. In TiC-TiO2 core-shell nanoparticle films TiO2 surface reactivity can be combined with TiC conductivity.     

Synthesis of small palladium nanoparticles stabilized by bisphosphine BINAP bearing an alkyl chain and their palladium nanoparticle-catalyzed carbon-carbon coupling reactions under room-temperature

A new bisphosphine ligand, C8-BINAP, and C8-BINAP-stabilized palladium nanoparticles have been prepared; C8-BINAP was found to be an effective protecting ligand for preparing and stabilizing palladium nanoparticles with very small core size and narrow size distribution and the C8-BINAP-Pd nanoparticles behave as an efficient catalyst for carbon-carbon coupling reactions at room temperature.     

Seed-mediated growth of palladium nanocrystals on indium tin oxide surfaces and their applicability as modified electrodes

Palladium nanoparticles (PdNPs) were successfully attached and grown on an indium tin oxide (ITO) surface using a seed-mediated growth method, i.e., via a simple two-step immersion of the ITO substrate into the seed and growth solutions. After the growth treatment for 24 h, PdNPs grew up to 60-80 nm, exhibiting crystal-like appearances and accompanying the formation of short rodlike nanocrystals as a minor product. Thus prepared PdNPs tend to stick each other, so that the dense gathering of PdNPs was observed on the ITO surfaces. Due to the dense attachment, the PdNPs directly attached to the ITO (PdNP/ITO) electrode had a significantly lowered charge-transfer resistivity compared with that of a bare ITO, and the redox reaction of [Fe(CN)6]3-/[Fe(CN)6]4- was observed as reversible in 0.1 M phosphate buffer solution. The electrocatalytic property of PdNPs was confirmed for the reduction of oxygen. In addition, some typical responses were observed in 0.5 M H2SO4 with the PdNP/ITO electrode, reflecting both the characteristics of NPs and the thin layer in nanoscale. The present preparation method of PdNP-attached surfaces would be promising for catalytic applications as well as electrochemical uses.