Site-Selective Supramolecular Complexation Activates Catalytic Ethane Oxidation by a Nitrido-Bridged Iron Porphyrinoid Dimer

Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 ⁵⁺, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 ⁵⁺ catalyzed ethane oxidation in the presence of H₂O₂ at a relatively low temperature. The site-selective complexation of 3 ⁵⁺ with an additional anionic porphyrin (TPPS⁴⁻) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 ⁵⁺ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS⁴⁻ to 3 ⁵⁺ enhanced the catalytic activity.     

Synthesis and characterization of molybdenum incorporated mesoporous aluminophosphate

A synthesis of molybdenum incorporated mesoporous aluminophosphate with long-chain n-alkylamine as template material had been prepared under non-aqueous condition. These materials were extensively characterized by using X-ray diffraction (XRD), nitrogen sorption isotherms, nuclear magnetic resonance of ²⁷Al and ³¹P (NMR), inductive coupled plasma (ICP), electron spin resonance (ESR), Fourier transform infrared (FTIR) and thermogravimetric-differential thermal analysis (TG-DTA). Morphology of the materials had been observed by using transmission electron microscope (TEM) that revealed the mesoporous materials possessed wormhole-like structures. Alkaline solvent extraction using n-butylamine/ethanol had been efficiently removed the n-alkylamine from the mesoporous samples which yielded BET surface areas around 550-730 m²/g. BJH analysis showed a narrow pore size distribution which increased with increasing of the carbon chain length of alkylamine (template). Valence state and coordination of the molybdenum in the obtained samples were investigated by using ESR and FTIR where it was found that Mo⁴⁺ and Mo⁶⁺ molybdenum species existed in the molybdenum incorporated mesoporous aluminophosphate in tetrahedral coordination.     

Dynamic and subjective responses of seated subjects exposed to simultaneous vertical and fore-and-aft whole-body vibration: The effect of the phase between the two single-axis components

Subjective and dynamic responses of seated subjects exposed to simultaneous vertical and fore-and-aft sinusoidal whole-body vibration were investigated. The effect of the phase difference between the vertical and the fore-and-aft vibration on the responses was of a particular interest in this study. Fifteen subjects were exposed to dual-axis vibrations at six frequencies (2.5-8 Hz) and at eight phases between the two single-axis components (0-315°). The magnitude of vibration in each axis was constant at 0.7 m s⁻² rms. Discomfort caused by vibration was measured by the method of magnitude estimation. The motion of the body were measured at the head and three locations along the spine with accelerometers attached to the body surface. The most significant effect of the phase between the two single-axis components on the discomfort was observed at 5 Hz: about 40% difference in the median discomfort estimate caused by changing the phase. The transmissibilities from vertical seat vibration to vertical motions of the spine varied from 0.5 to 2.0 by changing the phase between the two single-axis components at frequencies from 2.5 to 5 Hz. The effect of the phase observed in the dynamic response was not predicted by the superposition of the responses to each single-axis vibration. The discomfort caused by the dual-axis vibration tended to be correlated better with the combinations of the dynamic responses measured in the two axes than with the dynamic responses in a single axis.     

Drawing c-planar biconnected clustered graphs

In a graph, a cluster is a set of vertices, and two clusters are said to be non-intersecting if they are disjoint or one of them is contained in the other. A clustered graph C consists of a graph G and a set of non-intersecting clusters. In this paper, we assume that C has a compound planar drawing and each cluster induces a biconnected subgraph. Then we show that such a clustered graph admits a drawing in the plane such that (i) edges are drawn as straight-line segments with no edge crossing and (ii) the boundary of the biconnected subgraph induced by each cluster is a convex polygon.     

C-Fe chains due to segregated carbon impurities on Fe(1 0 0)

Bulk carbon impurities segregate at the Fe(1 0 0) surface and, upon thermal annealing, can form metastable surface phases with local and long range order and peculiar electronic properties. We present a surface science study of C-segregated Fe(1 0 0) with scanning tunneling microscopy, angle resolved photoemission, and ab initio calculations of the surface structure and electron states. In particular the c(3√2 × √2) structure, observed for 0.67 atomic layers of C segregated at the iron surface, is found to be due to self-organized carbon stripes made of zig-zag chains. The strong hybridization between C and Fe was observed in ARPES spectra.     

Internal Rotation of the Methyl Group in Cations of Toluene Derivatives

The potential of the internal rotation of the methyl group was determined for o-, m-, and p-fluorotoluene cations by pulsed field ionization spectroscopy. The potential of the internal rotational motion was also surveyed for other toluene derivative cations. It was found that the barrier height generally increases by ionization. The increase in the barrier height has been discussed in connection with the reduction of the internal rotational constant B by ionization. The geometrical distortion of the methyl group during the internal rotation has been suggested.