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.     

Precise measurement of magnetic moment of short-lived β-emitting nuclei12B ( I π=1+, T 1/2=20.18 ms)

The spin polarized β-emitting nuclei¹²B (I ^π=1⁺,T _1/2=20.18 ms) were produced by the nuclear reaction¹¹B(d, p)¹²B and by the selection technique of the incident deuteron energy and the¹²B recoil angle following the nuclear reaction. The nuclear magnetic moment of the short-lived nuclei¹²B was measured by β-NMR with the β-NMR and β-NQR setup established for the first time in China. The nuclear magnetic moment of¹²B was determined to be μ=0.99993±0.00048 nm org=0.99993±0.00048 after the precise correction of the Knight shift.     

Fabrication and transport properties of multiwall carbon nanotube crossroads

A multiwall carbon nanotube crossroads has been fabricated by a manipulation technique using a glass microcapillary, and the low temperature transport properties investigated. The two-terminal conductance of an individual tube shows Tomonaga–Luttinger liquid behavior G∝T^α at high temperature and dI/dV ∝V ^α at low temperature. However, no evidence of such a power-law behavior is obtained in the four-terminal conductance at the junction, where the conductance shows an almost metallic behavior ‘corrected’ by weak localization. Weak localization would essentially appear in electron states at the junctions of MWNTs.     

The Canonical Solutions of the Q-Systems¶ and the Kirillov–Reshetikhin Conjecture

We study a class of systems of functional equations closely related to various kinds of integrable statistical and quantum mechanical models. We call them the finite and infinite $Q$-systems according to the number of functions and equations. The finite Q-systems appear as the thermal equilibrium conditions (the Sutherland–Wu equation) for certain statistical mechanical systems. Some infinite Q-systems appear as the relations of the normalized characters of the KR modules of the Yangians and the quantum affine algebras. We give two types of power series formulae for the unique solution (resp. the unique canonical solution) for a finite (resp. infinite) Q-system. As an application, we reformulate the Kirillov–Reshetikhin conjecture on the multiplicities formula of the KR modules in terms of the canonical solutions of Q-systems. Received: 2 August 2001 / Accepted: 27 December 2001     

Experimental study of critical heat flux in open two-phase thermosyphon

Critical heat flux in an open two-phase thermosyphon has been measured employing water, R113 and R22 for a wide range ofL/D=4.8 to 960 and density ratio ofρ _L /ρ _G =6.17 to 1602. The CHF data measured, are found to be in fairly good agreement with those calculated from a criterion that the CHF takes place when reaches a maximum liquid falling rate in counter-current annular flow of liquid and vapor. Normal operation of the thermosyphon cannot be obtained at any liquid of water, R113 and R22 for a small tube diameter of less than 2 mm.     

Synthesis of a Stimuli‐Responsive P‐Chiral Polymer with Chiral Phosphorus Atoms and Azobenzene Moieties in the Main Chain

A reaction of the P‐chiral compound (S,S)‐1,2‐bis(boranato(tert‐butyl)methylphosphino)ethane with an azobenzene derivative gave stimuli‐responsive polymers with P‐chiral phosphines in the main chain. This is the first example of a stimuli‐responsive P‐chiral polymer. The polymer isomerized from the trans to the cis form upon UV irradiation and reverted to the trans form reversibly. The polymer was able to coordinate to platinum, and the resulting polymer complex exhibited the Cotton effect owing to the chirality of the phosphorus atoms. The structure of the P‐chiral polymer obtained could be changed reversibly by light and thermal stimuli, and the polymer chain was induced to rotate helically when complexed with transition metals through the chiral phosphorus atoms.     

Effect of methotrexate treatment on the onset of autoimmune kidney disease in lupus mice.

In the present study, we examined the effects of methotrexate (MTX) on the development of autoimmune kidney disease in three kinds of autoimmune prone mice, NZB/NZW F1 (BWF1) mice, MRL/Mp-lpr/lpr (MRL/lpr) mice and NZW/BXSB F1 (WBF1) mice. The results showed that MTX delayed the appearance of proteinuria and prolonged survival of both BWF1 and MRL/lpr mice and inhibited the elevation of blood urea nitrogen (BUN) levels which accompanies the development of lupus nephritis. However, MTX treatment did not affect these in WBF1 mice. Furthermore, MTX could not suppress immunoglobulin G (IgG) class anti-deoxyribonucleic acid (DNA) and anti-trinitrophenol (TNP) antibody production in any variety of mice. These suggest that the therapeutic effect of MTX on BWF1 and MRL/lpr mice does not result in the suppression of IgG autoantibody production.     

Structural variety of membrane permeable peptides

Peptide-mediated protein delivery into living cells has been attracting our attention. Among the peptides that have been reported to have carrier activity, the one from the human immunodeficient virus (HIV)-1 Tat has been most often used for the introduction of exogenous macromolecules into cells. We have shown that not only the Tat peptide, but also various arginine-rich peptides showed very similar characteristics in translocation, and the possible presence of ubiquitous internalization mechanisms among the arginine-rich peptides has also been suggested. These arginine-rich peptides includes ones derived from HIV-1 Rev and flock house virus coat proteins. The linear- and branched-chain peptides containing approximately 8 residues of arginine also show a similar ability. In this review, we present the structural variety of membrane permeable peptides and provide a survey of the findings on the translocation of these peptides through the cell membranes.     

Suppressive effect of the SOS-inducing activity of chemical mutagen by citric acid esters from Prunus mume Sieb. Et Zucc. using the Salmonella typhimurium TA1535/pSK1002 umu test

A methanol extract from Prunus mume Sieb. Et Zucc. showed a suppressive effect of the SOS-inducing activity on the mutagen 3-amino-1,4-dimethyl-SH-pyrido[4,3-b]indole(Trp-P-1) in the Salmonella typhimurium TA1535/pSK1002 umu test. The methanol extract was re-extracted with hexane, dichloromethane, ethyl acetate, butanol and water. The dichloromethane and ethyl acetate fractions showed suppressive effect. Suppressive compounds were isolated by silica gel column chromatography and identified as trimethyl citrate (1) and dimethyl citrate (2) by GC-MS, IR and 1H and 13C-NMR spectroscopy. Compounds 1 and 2 suppressed 51 and 39% of the SOS-inducing activity at a concentration of 2.0 micromol/mL.