A novel tripodal ligand, tris[(4'-methyl-2,2'-bipyridyl-4-yl)methyl]carbinol and its trinuclear Ru(II)/Re(I) mixed-metal complexes: synthesis, emission properties, and photocatalytic CO2 reduction

A novel tripodal ligand, tris[(4'-methyl-2,2'-bipyridyl-4-yl)methyl]carbinol (L), has been synthesized. The spectroscopic, electrochemical, and photocatalytic properties of the new trinuclear complexes (Ru(2)Re and RuRe(2)) linked by the tripodal bridging ligand L are then investigated. In addition, 2-fold-improved photocatalytic activities were obtained in the case of these trinuclear complexes compared to the mixtures of the appropriate monometallic model complexes in the reduction of CO(2) under visible irradiation.     

Highly polarized very cold neutrons through a permanent magnet quadrupole

We obtained highly polarized very cold neutrons through a quadrupole magnet with a large aperture. When neutrons go through a quadrupole magnet, parallel-spin neutrons are attracted to the magnet axis and anti-parallel-spin neutrons are repelled off the axis. Therefore, the neutrons through a sufficiently long quadrupole magnet have completely parallel-spin. At the downstream of the quadrupole magnet, we placed another quadrupole magnet to divide neutrons into two regions depending on their spin directions. We obtained the neutron polarization from the integrated count of the two regions and found it was 99.88±0.09 (stat.)±0.05 (syst.)%.     

Carbon-13 NMR Spectra of Peracetylated Derivatives of Methyl L-Arabinofuranoside and Oligosaccharides Related to Arabinoxylan

Abstract

The ¹³C NMR signals of methyl tri-O-acetyl-l-arabinofuranosides were assigned on the basis of heteronuclear shift correlated NMR spectra. From the enzymic digest of barley-hull arabinoxylan two oligosaccharides, i.e., α-l-Araf-(1→3)-β-d-xylp-(1→4)-d-xylp and α-l-Araf-(1→3)-β-d-xylp-(1→4)-β-d-xylp-(1→4)-d-xylp were obtained. The NMR spectra of their per-O-acetylated derivatives were assigned, and discussed.     

X-ray photoelectron spectroscopic studies on oxidation behavior of nickel and iron aluminides under oxygen atmosphere at low pressures

Oxidation behaviors of NiAl, Ni₃Al, and FeAl under oxygen atmosphere at low pressures were studied by X-ray photoelectron spectroscopy (XPS). Clean surfaces of these aluminides were prepared by fracturing in an ultra high vacuum, and then the fractured surfaces were oxidized by exposing to high-purity oxygen at pressures up to 1.3 Pa without exposing to air. The oxides formed on NiAl and FeAl surfaces were Al₂O₃, whereas the oxide on Ni₃Al was NiAl₂O₄. Aluminum, nickel, and iron on clean surfaces were oxidized even at a pressure of 1.3 × 10⁻⁶ Pa. The oxidation evolves with an increase in the pressure of oxygen, and further oxidation of aluminum occurs prior to that of nickel or iron. The oxidation behaviors under such oxygen atmosphere were similar to those of the aluminides oxidized in air, and these behaviors could be predicted from thermodynamic consideration.     

Formation and Structure of Cluster-Included Carbon Nanocapsules Prepared by Polymer Pyrolysis

Abstract

Formation of carbon nanocapsules with various clusters (SiC, Au, Fe. Co. Ge. and GeO₂) by polymer pyrolysis was investigated, and nanocapsules with SiC and Au nanoparticles were produced by thermal decomposition of polyvinyl alcohol at ?500°C in Ar gas atmosphere. The formation mechanism of nanocapsules and a structural model for the nanocapsule/SiC interface were proposed. In addition, carbon clusters were formed at the surface of carbon nanocapsules, and carbon onions were produced by electron irradiation of amorphous carbon produced from polyvinyl alcohol. The present work indicates that the pyrolysis of polymer materials with clusters is a useful fabrication method for the mass-production of carbon nanocapsules and onions at low temperatures compared to the ordinaly are discharge method.     

Versatile synthesis of fluorescent, cross-linked peptides as biological probes with the advantage of high helix content

A variety of fluorophores were introduced at the N-termini of short peptides for use as biological-probes. The fluorescent peptides were cross-linked with a diacetylenic cross-linking agent between the amino acid side chains of ornithine (Orn) residues to produce peptides with high helix content.     

Effects of a cap layer on built-in electric fields of AlxGa1-xN/GaN heterostructures non-destructively probed by Franz-Keldysh oscillations

We have investigated electric field strengths in the Al_xGa_1-xN layer, F_AlGaN's, of Al_xGa_1-xN/GaN heterostructures with and without a GaN cap layer using photoreflectance (PR) spectroscopy. Franz-Keldysh oscillations (FKOs) from the Al_xGa_1-xN layer are clearly observed in the PR spectra. It is found from analysis of the FKOs that stacking of the cap layer causes a remarkable enhancement of F_AlGaN. This fact demonstrates that the FKO profile is a non-destructive probe for a change of built-in electric field strength induced by a cap layer. Numerical calculations of F_AlGaN based on a Schr?dinger-Poisson equation clarify that the magnitude of the enhancement of F_AlGaN is dominated by the cap-layer thickness.     

Hydrogen storage in boron nitride and carbon clusters studied by molecular orbital calculations

Possibility of hydrogen gas storage in carbon (C) and boron nitride (BN) clusters was investigated by molecular orbital calculations. Chemisorption calculation was carried out for C₆₀, B₂₄N₂₄ and B₃₆N₃₆ with changing position of hydrogen atom to compare the bonding energy at carbon, nitrogen and boron, tetragonal and hexagonal rings. Chemisorption calculation of hydrogen for BN clusters showed that hydrogen bondings with nitrogen atoms and tetragonal rings were the most stable. Stability of H₂ molecules inside BN and C clusters was also investigated by molecular orbital calculations. C and BN clusters showed possibility of hydrogen storage of 6.5 and 4.9 wt%, respectively.     

Substituted propenyl end groups as reactive intermediates in radical polymerization

The addition of propagating radicals of methyl acrylate (MA) and styrene (St) to CH₂?C(CO₂CH₃)CH₂? and CH₂?C(C₆H₅)CH₂? ω‐end groups of poly(methyl methacrylate) (PMMA) and polystyrene (PSt) was investigated. The end groups were as reactive as MA and St toward the poly(methyl acrylate) (PMA) and PSt radicals, respectively. The adduct radical derived from the two types of PMMA end groups and PMA radicals underwent β fragmentation exclusively to yield PMMA radicals and end groups bound to PMA chains. The addition of PSt radicals to PMMA with CH₂?C(CO₂Me)CH₂? end groups resulted in adduct radicals that underwent β fragmentation and addition to St or coupling with PSt radicals. Adduct radicals formed by the addition of PMA radicals to both types of end groups of PSt exclusively formed C? C bond by coupling with PMA radicals to form branched structures or by addition to MA monomer to give a copolymer. The fate of the adduct radicals was highly dependent on the type of polymer chain and the substituent bound to the end group. Steric congestion of the adduct radical arising from the α‐methyl group of the PMMA chain was considered to be crucial for fragmentation to expel the PMMA radical. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 645–654, 2003     

Synthesis and Photochemical Properties of Covalently-Linked Dimers of Ruthenium(II) Tris (Bipyridine) Complex: Comparison with Ru(II)(bpy)2 (Poly-4-Methyl-4′-Vinylbipyridine)

Covalently linked dimers of Ru(bpy)₃ ²⁺ (3 and 4) connected by two or three carbon atoms were synthesized as models for Ru(bpy)₃ ²⁺-containing vinyl polymer (1). The luminescence properties of 3 and 4 were compared with those of its component monomer, 4,4′-dimethyl-2,2′-bipyridine-bis(2,2′-bipyridine)ruthenium(II) complex (2). In excited 3 and 4, intramolecular interaction leading to enhanced quenching was not observed. Electron-transfer quenching of the excited dimer with methylviologen (MV²⁺) and the zwitterionic viologen, 1,1′-bis(3-sulfopropyl)4,4′-bipyridinium (SPV), was studied and compared with that of 1 and 2. The low quenching efficiency in 1, 3, and 4 systems can be ascribed to the steric hindrance of unexcited ruthenium complex. Energy migration between ruthenium complexes in the excited 1, 3, and 4 can be ruled out from the kinetic evidence.