Depth estimation of protoporphyrin IX objects in turbid media considering the fluorescence intensity ratio between two wavelengths of light for application in invasion diagnosis of gastric cancer

Optical Review - This paper demonstrates a method to estimate the depth of a fluorescence object in turbid media using dual-wavelength excited photodynamic diagnosis, to aid in the invasion depth...     

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.     

Selective Propargylation of Carbonyl Compounds and Imines with Barium Reagents

A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13.     

Estimation of growth rate in unidirectionally solidified multicrystalline silicon by the growth-induced striation method

Multicrystalline silicon was grown by unidirectional solidification method using the accelerated crucible rotation technique. The application of the accelerated crucible rotation technique in unidirectional solidification method induced growth striations across the axial direction of the grown crystal. This striation pattern was observed from carbon concentration distribution, obtained by using Fourier transform infrared spectroscopy. The generated striation pattern was found to be weak and discontinuous. Some striations were absent, probably due to back melting, caused during each crucible rotation. From the growth striations and applied time period in crucible rotation, the growth rate was estimated by using Fourier transformation analysis.     

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.     

Preparation of macromonomers by copolymerization of methyl acrylate dimer involving β fragmentation

The unsaturated dimer of methyl acrylate [CH₂C(CO₂CH₃)CH₂CH₂CO₂CH₃, or MAD] was copolymerized with various monomers to prepare copolymers bearing the ω-unsaturated end group [CH₂C(CO₂CH₃)CH₂ ] arising from β fragmentation of the MAD propagating radical. Copolymerizations of MAD with cyclohexyl and n-butyl acrylate resulted in copolymers with ω-unsaturated end groups, and increasing the temperature up to 180 °C resulted in an increase in the rate of β fragmentation of MAD radicals relative to propagation. Only a small amount of unsaturated end groups was introduced by copolymerization with ethyl methacrylate (EMA), and the EMA content in the copolymer increased with temperature. These findings could be explained by the reversible addition of the poly(EMA) radical to MAD. The copolymerization with ethyl α-ethyl acrylate (EEA) did yield a copolymer containing unsaturated end groups with MAD units as part of the main chain, although the steric hindrance of the ethyl group suppressed homopropagation and crosspropagation of EEA, resulting in low polymerization rates. Therefore, the copolymerization of MAD with acrylic esters at high temperatures was noted as a convenient route for obtaining acrylate–MAD copolymers bearing unsaturated end groups at the ω end (macromonomer). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 597–607, 2004