ESR Study of a Nitroxide Radical in Sol-Gel Glasses

A spin probe TEMPOL (4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxy) was dissolved in a tetraethyl orthosilicate sol-gel reaction system and measured by electron spin resonance spectroscopy at 295 K. The nitrogen hyperfine coupling constant was from 1.64–1.66 mT in the sol-gel solutions. The values were sensitive to the ethanol-to-water ratio of the solutions. The hyperfine coupling constant in the xerogels was 1.70 mT, which was almost the same as that in water, indicating that the probe molecules were trapped in silica pores with water adsorbed on the silica surfaces. The motion of TEMPOL in the xerogels was considerably slower than in the sol-gel solutions. The local viscosity estimated was from 70–90 cP. The ESR spectra of TEMPOL were altered during the sol-gel process, indicating that adsorbed water on the silicas surfaces has an important role for trapping organic molecules in sol-gel glasses.     

Water cluster growth in hydrophobic solid nanospaces

The growth mechanism of water clusters in carbon nanopores is clearly elucidated by in situ small-angle X-ray scattering (SAXS) studies and grand canonical Monte Carlo (GCMC) simulations at 293-313 K. Water molecules are isolated from each other in hydrophobic nanopores below relative pressures (P/P(0)) of 0.5. Water molecules associate with each other to form clusters of about 0.6 nm in size at P/P(0)=0.6, accompanied by a remarkable aggregation of these clusters. The complete filling of carbon nanopores finishes at about P/P(0)=0.8. The correlation length analysis of SAXS profiles leads to the proposal of a growth mechanism for these water clusters and the presence of the critical cluster size of 0.6 nm leads to extremely stable clusters of water molecules in hydrophobic nanopores. Once a cluster of the critical size is formed in hydrophobic nanopores, the predominant water adsorption begins to fill carbon nanopores.     

Photosensing Device Composed of Bilayer Membranes of Polymer-Pendant Ru(bpy)3 2+ and Prussian Blue

A photosensing device was fabricated based on a photochemical electron transfer reaction. A graphite electrode was coated with bilayer membranes of polymer-pendant Ru(bpy)₃ ²⁺ and Prussian Blue (PB) to give a bilayer-coated device. It was irradiated with visible light in an aqueous electrolyte and the induced photocurrent was measured as a function of the applied potential. The excitation of PB was responsible for the anodic photocurrent, while the excitation of the Ru complex mainly induced the cathodic photocurrent by an electron-transfer mechanism.     

Application of Polymer-Embedded Tris(2,2′ Bipyridine-Ruthenium(II) to Photodetection of Oxygen

A Nafion film containing tris(2,2′-bipyridine)ruthenium(II) as a luminescence probe was applied to photodetection of oxygen in a gas by utilizing the luminescence quenching by dioxygen. The linear Stern-Volmer plots of the emission intensity with respect to the oxygen concentration allowed quantitative determination of the oxygen. From the emission decay studied by a single-photon counting method, it was concluded that the quenching of the excited state Ru complex by oxygen proceeds by a conventional dynamic mechanism.     

Convenient Method for Dehalogenation of Aryl Halides

Reductive dehalogenation of aryl halides was achieved using hydrogen and a palladium catalyst. By using deuterium gas, the deuterated arenes were readily prepared.     

CHARACTERISTIC PROPERTIES OF LECITHIN AS A SURFACTANT

Characteristic solution properties of lecithin were studied in 1) water+propanol/lecithin/hexadecane and 2) ethanol/lecithin/ hexadecane systems. 1) Solvent property of water changes by added alcohol and the hydrophile-lipophile property of lecithin is balanced in 13 wt% propanol aq.-hexadecane system. Three liquid phases, i.e. aqueous alcohol, lecithin and hexadecane are found. The volume fraction of the lecithin phase increases with its concentration and at 2.3 wt%/system, all solvent molecules are swelled and one microemulsion phase is obtained. 2) In ethanol/ lecithin/hexadecane system, lecithin is also insoluble in the solvent, and swells a large amount of hexadecane.     

Transportation of a microdroplet on an oriented liquid crystal surface

Wetting phenomena play important roles in several technological applications and in many physical and biological thin‐film phenomena, such as wetting, adhesion and friction. One of key issues of these studies is to control the surface energy (or wettability) dynamically for liquid transportation. We have developed a liquid crystal (LC) surface for use as a transport substrate since we expected that the surface energy of an LC surface can be controlled rapidly using an electric field. The rapid control of the polarisability (or wettability) of a liquid crystalline surface by an electric field has been demonstrated, together with the transportation of a liquid microdroplet.     

Synthesis,Structure, and Reactivity of Lewis Base Stabilized Plumbacyclopentadienylidenes

Plumbacyclopentadienylidenes, in which the lead atoms have divalent states and are coordinated by THF, pyridine and N‐heterocyclic carbene, were synthesized and characterized. The THF‐ and pyridine‐stabilized compounds can be regarded as rare examples of hypervalent 10‐X‐4 species. The equilibrium between the THF adduct and the free plumbacyclopentadienylidene was evidenced by spectroscopic analysis and theoretical calculations. The THF adduct in benzene converted into a plumbylene dimer, where one of the lead centers is coordinated by THF and the other lead atom is coordinated by a divalent lead atom, the dimer gradually decomposing into spiroplumbole. The THF adduct unexpectedly reacted with trifluoroborane and trichlorogallane to afford fluoroborole and chlorogallole, which are the first examples of non‐annulated fluoroborole and gallole, respectively.     

Multiple plasmonic effect on photocurrent generation of metal‐loaded titanium dioxide composite/dye films on gold grating surface

We demonstrate the multiple plasmonic effect on the photocurrent properties of photoanodes containing Ag or Au nanoparticles (NPs) loaded onto titanium dioxide film (Ag–TiO₂ or Au–TiO₂) on Au grating surfaces. Ag–TiO₂ or Au–TiO₂ nanocomposite particles are prepared by a flame spray pyrolysis route. The structures and morphologies of the prepared products are characterized by high‐resolution transmission electron microscopy. The Ag–TiO₂ or Au–TiO₂ composite NPs are deposited by spin coating onto the Au grating surfaces. The photoanode electrode is a layered structure of blu‐ray disc‐recordable grating substrate/Au/Ag (or Au)–TiO₂/dye/electrolyte/indium‐tin oxide. The plasmonic effect is induced when Ag or Au NPs are located within the propagating surface plasmon (SP) field on the Au grating surface. The short‐circuit photocurrent is increased by exciting the grating‐coupled propagating SP on the Au gratings and is further enhanced by positioning the Ag or Au NPs within the grating‐coupled SP field. Copyright © 2014 John Wiley & Sons, Ltd.     

Application of the single comparator method to instrumental photon activation analysis

Journal of Radioanalytical and Nuclear Chemistry - Instrumental photon activation analysis (IPAA) is nondestructive and multi-elemental analysis method like instrumental neutron activation...