Hydrophobicity parameters determined by reversed-phase liquid chromatography. XVI: A new hydrogen-accepting parameter for monosubstituted thiophenes and furans for correlating retention factors and octanol-water partition coefficients

We recently proposed a new hydrogen-accepting parameter, S(HA), for monosubstituted (di)azines on the basis of the heat of formation calculated by the conductor-like screening model (COSMO) method. In this work, S(HA) values for monosubstituted thiophenes and furans were calculated and the results were applied to the analysis of relationships between log P (P: 1-octanol/water partition coefficient) and log k (k: retention factor obtained by reversed phase HPLC). The S(HA) parameter was found to work effectively as a hydrogen-bonding parameter in a range of heteroaromatic compounds.     

Near-field optical imaging of plasmon modes in gold nanorods

We have investigated optical properties of single gold nanorods by using an apertured-type scanning near-field optical microscope. Near-field transmission spectrum of single gold nanorod shows several longitudinal surface plasmon resonances. Transmission images observed at these resonance wavelengths show oscillating pattern along the long axis of the nanorod. The number of oscillation increases with decrement of observing wavelength. These spatial characteristics were well reproduced by calculated local density-of-states maps and were attributed to spatial characteristics of plasmon modes inside the nanorods. Dispersion relation for plasmons in gold nanorods was obtained by plotting the resonance frequencies of the plasmon modes versus the wave vectors obtained from the transmission images.     

Morphological and spectroscopic properties of thin films of self-assembling amphiphilic porphyrins on a hydrophilic surface as revealed by scanning near-field optical microscopy

We fabricated porphyrin thin films on mica surfaces from acidic aqueous solutions of the preorganized H-aggregates of amphiphilic porphyrins by the simple spin-coating method. The morphological and spectroscopic properties of the film were investigated by scanning near-field optical microscopy. The results obtained in this study demonstrate that the preorganized structure in solution can be transferred as a thin film with a thickness of the monolayer level without losing their substantial structure and photophysical properties.     

Controlled hydrogenation of diphenylacetylene using alkylammonium formate

A simple and straightforward semihydrogenation of alkyne to alkene with triethanolamine and formic acid in the presence of PdCl₂ has been described. Although hydrogenation using formic acid as a hydrogenation source has been used in combination with amines previously, few reports are available concerning the associated reactivity. We demonstrated that reactivity changes depending on the type of amine used in the hydrogenation. Further, this reaction requires no strict time control, making it a useful tool in organic synthesis.     

Nanoporous ultra-high-entropy alloys containing fourteen elements for water splitting electrocatalysis

High-entropy alloys (HEAs) are near-equimolar alloys comprising five or more elements. In recent years, catalysis using HEAs has attracted considerable attention across various fields. Herein, we demonstrate the facile synthesis of nanoporous ultra-high-entropy alloys (np-UHEAs) with hierarchical porosity via dealloying. These np-UHEAs contain up to 14 elements, namely, Al, Ag, Au, Co, Cu, Fe, Ir, Mo, Ni, Pd, Pt, Rh, Ru, and Ti. Furthermore, they exhibit high catalytic activities and electrochemical stabilities in the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in acidic media, superior to that of commercial Pt/graphene and IrO₂ catalysts. Our results offer valuable insights for the selection of elements as catalysts for various applications.

Nanoporous ultra-high-entropy alloys containing 14 elements (Al, Ag, Au, Co, Cu, Fe, Ir, Mo, Ni, Pd, Pt, Rh, Ru, and Ti) were obtained by dealloying. The products showed excellent electrocatalytic performance for water splitting in acidic media.     

Membrane Preparation of Polysulfonic Acid Complexes by Layer-by-Layer Adsorption

Summary: The water-insoluble, thermostable and homogeneous polymer complex membrane formation of polysulfonic acids was examined by modifying the preparation conditions of the layer-by-layer adsorption method of the acid and base polymers. The complexation of poly(4-styrenesulfonic acid) in the 0.15 unit mM solution with poly(allylamine) gave a polymer complex membrane on a gold substrate in which one polymer layer was formed with a thickness of 1 nm. Properties including the proton conductivity of the membrane suggested possible applications of the polymer complex membrane.     

Oxygen-binding to simple cobaltporphyrins combined with polyvinylmidazole

Reversible oxygen-binding was observed at low temperature for the poly(vinylimidazole-co-octyl methacrylate) complexes of the simple or planar cobaltporphyrins (CoP) such as cobalt-tetraphenylporphyrin and cobalt-octaethylporphyrin. The oxygen-binding affinity and rate constants were compared with those for the cobalt-picketfence porphyrin, a typical oxygen-carrier. The low oxygen-binding affinity for the CoP complexes was attributed to the enormously large oxygen-releasing rate constant.