Chiral Interlocked Corrole Dimers Directly Linked at Inner Carbon Atoms of Confused Pyrrole Rings

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.     

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.     

Binding position of azathioprine with bovine serum albumin determined by measuring nuclear magnetic resonance relaxation time.

The interaction between azathioprine (AZ) and bovine serum albumin (BSA) is mainly due to hydrophobic binding according to the dependence of the binding constant on the ionic strength obtained by equilibrium dialysis. The binding constant and partition coefficient of AZ were smaller than those of warfarin, phenylbutazone and ibuprofen. Little variation in the proton chemical shift of AZ was observed whether there was an absence or presence of BSA (7.25 x 10(-5) M). The spin-lattice relaxation time (T1) of AZ decreased in the presence of BSA to 6-22%. The spin-spin relaxation rate (1/T2) of AZ increased 16-24 times for the methyl group and the imidazole ring and 8-13 times for the purine ring in the presence of BSA. The ratio of the spin-spin relaxation rate of the free AZ to the bound AZ ((1/T2)b/(1/T2)f) of the methyl group and the imidazole ring was 2-3 times larger than that of the purine ring. The binding of AZ to BSA was concluded to be mainly at the methyl group on the imidazole ring of AZ.     

A stability of the steady flow of compressible viscous fluid with respect to initial disturbance (v∞ ≠ 0)

We consider a compressible viscous fluid with the velocity at infinity equal to a strictly non‐zero constant vector in ?³. Under the assumptions on the smallness of the external force and velocity at infinity, Novotny–Padula (Math. Ann. 1997; 308 :439– 489) proved the existence and uniqueness of steady flow in the class of functions possessing some pointwise decay. In this paper, we study stability of the steady flow with respect to the initial disturbance. We proved that if H³‐norm of the initial disturbance is small enough, then the solution to the non‐stationary problem exists uniquely and globally in time, which satisfies a uniform estimate on prescribed velocity at infinity and converges to the steady flow in L_q‐norm for any number q? 2. Copyright © 2006 John Wiley & Sons, Ltd.     

Homohelicity induction of propylene-linked zinc bilinone dimers by complexation with chiral amine and α-amino esters. Preorganization of structurally coupled homohelical subunits

Homohelicity induction of a series of propylene-linked zinc bilinone (ZnBL; linear tetrapyrrople-zinc(II) complex) dimers upon complexation with chiral amine and α-amino esters was investigated. Introduction of substituents such as dimethyl and diisobutyl to the central carbon of the propylene spacer gave rise to stabilization of the homohelical (PP and MM) conformers rather than the heterohelical (PM) conformer. As bulkiness of the substituent increased, stability of the homohelical conformers was raised. The preorganization of the homohelical structures led to significantly amplified homohelicity induction upon complexation with chiral amine and α-amino esters.     

Reaction of C3 and C4 ketoses with alkenals and alkenones in water

Treatment of 1,3-dihydroxyacetone and acrolein with aqueous KOH gave a tetrahydrofuran derivative, 1,4-dihydroxy-3,7-dioxabicyclo[3.3.0]octane, in 80% yield. Similarly, 6-alkyl substituted 1,4-dihydroxy-3,7-dioxabicyclo[3.3.0]octanes were obtained by reaction of 1,3-dihydroxyacetone with various α,β-unsaturated aldehydes. In the cases of long chain alkenals, the reaction was effectively accelerated in the presence of organic co-solvent. On the other hand, the corresponding tricyclic products were synthesized by reaction of 1,3-dihydroxyacetone with cyclic enones, such as 2-cyclopentenone and 2-cyclohexenone. This method was successfully applied to the reaction of a tetrulose in the absence of any protecting groups.     

Real-time monitoring of the desorption process of chlorine-covered Si(111)-‘1×1’ surface with second-harmonic generation

To elucidate the fundamental process underlying the semiconductor surface fabrication, isothermal desorption from a Cl/Si(111)-‘1×1’ surface was monitored by means of second-harmonic generation with 1064 nm light. During the desorption, surface Cl-coverages were obtained in real time. The temperature dependence of the desorption rates revealed that the energy barrier against chloride desorption is 2.1 eV. A very slow second phase in the recovery of the second-harmonic intensity is associated with reconstruction of 7×7 DAS structure following the desorption. The activation energy for the reconstruction was 2.4 eV.     

Trinucleon cluster structure at high-excitation energies in A=6 nuclei

Trinucleon molecular structures in ⁶He and ⁶Be were investigated by using the ⁶Li(⁷Li, ⁷Be)⁶He reaction at 455 MeV and ⁶Li(³He, t)⁶Be reaction at 450 MeV, respectively. Binary decays into t + t from a broad state at E _x =18.0±1.0 MeV in ⁶He and into ³He + ³He from one at E _x =18.0±1.2 MeV in ⁶Be, respectively, were observed by measuring trinucleon cluster decays in coincidence with reaction particles. The branching ratios for binary decay were estimated to be about 0.7 for ⁶He and ⁶Be. These large branching ratios show that a trinucleon cluster state exists as an isobaric partner around E _x =18 MeV in ⁶He and ⁶Be.     

A new method for atmospheric nitrogen dioxide measurements using the combination of a stripping coil and fluorescence detection.

A new stripping coil for the collection of nitrogen dioxide (NO2) has been developed to increase its versatility and efficiency. Nitrogen dioxide measurements based on quantitative collection through a reaction coil into an alkaline solution has been examined. Nitrogen dioxide is collected in a 0.1 N NaOH solution. This collection system has an efficiency of nearly 100%. The absorbed nitrogen dioxide has been measured by fluorescence detection with sub-ppbv detection limits. The excitation wavelength at 360 nm and the produced emission wavelength at 405 nm were suitable for nitrite ion measurements.