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711.
High-resolution electron spin resonance (ESR) spectra of radical pairs of a hydrogen atom that coupled with a methyl radical (H...CH3, H...CHD2, D...CH2D, and D...CD3) were observed for X-ray irradiated solid argon containing selectively deuterium-labeled methanes, CH4, CH2D2, and CD4, at 4.2 K. The double-quartet 1H-hyperfine (hf) splittings of ca. 26 and 1.16 mT at the Deltam(s) = +/-1 and Deltam(s) = +/-2 transitions, which are one-half of the isotropic 1H-hf splittings of an isolated H-atom and a CH3 radical, were attributed to the H...CH3 pair. The 1H-hf splittings at the Deltam(s) = +/-1 transition were further split by the fine structure (fs) due to the electron dipole-dipole coupling. Because of the high-resolution spectra, three different sets of the fs splitting, d, are clearly resolved in the spectra of both the H...CH3 and the D...CD3 pairs. The separation distance (inter-spin distance), R, between the H-atom and the CH3 radical being in pairs was evaluated from the d values based on a point-dipole interaction model. For the case of the H...CH3 pair, the observed d values of 4.2, 4.9, and 5.1 mT yield the respective separations, R = 0.87, 0.83, and 0.82 nm, to probe the trapping site of the pair in an Ar crystalline lattice (fcc). For the pair with R = 0.87 nm, for example, we propose that the CH3 radical occupies a substitutional site and the counter H-atom occupies either the interstitial tetrahedral sites directed away from the CH3 radicals by a distance of 0.87 nm or the interstitial octahedral sites by a distance of 0.88 nm. When a mixture of CH4 and CD4 in a solid Ar matrix was irradiated, only two different radical pairs, H...CH3 and D...CD3, were observed. This result clearly demonstrates that the hydrogen atom and methyl radicals, which undergo a pairwise trapping, can originate from the same methane molecule. 相似文献
712.
A new class of polymerizations was developed via metal-catalyzed C-C bond forming radical polyaddition; the monomers were designed to have a reactive C-Cl bond, which can be activated by the metal catalysts to generate a carbon radical species, along with a C=C double bond, to which the carbon radical generated from another molecule adds to form a C-C backbone polymer with an inactive C-Cl pendant. 相似文献
713.
Sato S Sekine A Ohashi Y Ishitani O Blanco-Rodríguez AM Vlcek A Unno T Koike K 《Inorganic chemistry》2007,46(9):3531-3540
Excitation by high-energy light, such as that of 313 nm wavelength, induces a photochemical ligand substitution (PLS) reaction of fac-[Re(bpy)(CO)3Cl] (1a) to give the solvento complexes (OC-6-34)- and (OC-6-44)-[Re(bpy)(CO)2(MeCN)Cl] (2 and 3) in good yields. The disappearance quantum yield of 1a was 0.01+/-0.001 at 313 nm. The products were isolated, and X-ray crystallographic analysis was successfully performed for 2. Time-resolved IR measurements clearly indicated that the CO ligand dissociates with subpicosecond rates after excitation, leading to vibrationally hot photoproducts, which relax within 50-100 ps. Detailed studies of the reaction mechanism show that the PLS reaction of 1a does not proceed via the lowest vibrational level in the 3MLCT excited state. The PLS reaction gives 2 and (OC-6-24)-[Re(bpy)(CO)2(MeCN)Cl] (5) as primary products, and one of the products, 5, isomerizes to 3. This type of PLS reaction is more general, occurring in various fac-rhenium(I) diimine tricarbonyl complexes such as fac-[Re(X2bpy)(CO)3Cl] (X2bpy=4,4'-X2-bpy; X=MeO, NH2, CF3), fac-[Re(bpy)(CO)3(pyridine)]+, and fac-[Re(bpy)(CO)3(MeCN)]+. The stable photoproducts (OC-6-44)- and (OC-6-43)-[Re(bpy)(CO)2(MeCN)(pyridine)]+ and (OC-6-32)- and (OC-6-33)-[Re(bpy)(CO)2(MeCN)2]+ were isolated. The PLS reaction of rhenium tricarbonyl-diimine complexes is therefore applicable as a general synthetic method for novel dicarbonyls. 相似文献
714.
Koshiyama A Ichibangase T Moriya K Koike K Yazawa I Imai K 《Journal of chromatography. A》2011,1218(22):3447-3452
A wide-pore (30 nm) reversed-phase column (Intrada WP-RP, particle size 3 μm) was recently utilized for protein separation in differential proteomics analysis with fluorogenic derivatization-liquid chromatography-tandem mass spectrometry (FD-LC-MS/MS), and exerted a tremendous effect on finding biomarkers (e.g., for breast cancer). Further high-performance separation is required for highly complex protein mixtures. A recently prepared non-porous small-particle reversed-phase column (Presto FF-C18, particle size: 2 μm) was expected to more effectively separate derivatized protein mixtures than the wide-pore column. A preliminary experiment demonstrated that the peak capacity of the former was threefold greater than that of the latter in gradient elution of a fluorogenic derivatized model peptide, calcitonin. The FD-LC-MS/MS method with a non-porous column was then optimized and applied to separate liver mitochondrial proteins that were not efficiently separated with the wide-pore column. As a result, high-performance separation of mitochondrial proteins was accomplished, and differential proteomics analysis of liver mitochondrial proteins in a hepatitis-infected mouse model was achieved using the FD-LC-MS/MS method with the non-porous column. This result suggests the non-porous small-particle column as a replacement for the wide-pore column for differential proteomics analysis in the FD-LC-MS/MS method. 相似文献
715.
Sasaki T Li W Morimura H Li S Li Q Asada Y Koike K 《Chemical & pharmaceutical bulletin》2011,59(11):1396-1399
The MeOH extract from the whole plants of Sambucus adnata has shown significant protein-tyrosine phosphatase 1B (PTP1B) inhibitory activity. Chemical study on the extract resulted in the isolation of thirteen compounds, including a novel triterpene (1). The structure of 1 was determined to be 1α,3β-dihydroxy-urs-12-en-11-one-3-yl palmitate on the basis of extensive spectroscopic analyses. Among the isolated compounds, ursolic acid, oleanolic acid and (±)-boehmenan showed the most potent PTP1B inhibitory activity in vitro with the IC(50) values of 4.1, 14.4 and 43.5 μm, respectively. The kinetic analysis indicated that (±)-boehmenan inhibits PTP1B activity in a competitive manner. 相似文献
716.
The coating of TiO(2) particles (P25) by a nanoporous silica layer was conducted to impart molecular recognitive photocatalytic ability. TiO(2)/nanoporous silica core/shell particles with varied pore diameters of the shell were synthesized by the reaction of P25 with an aqueous mixture of tetraethoxysilane and alkyltrimethylammonium chloride with varied alkyl chain lengths, followed by calcination. The TEM and nitrogen adsorption/desorption isotherms of the products showed that a nanoporous silica shell with a thickness of ca. 2nm and controlled pore diameter (1.2, 1.6, and 2.7 nm) was deposited on the titania particle when surfactants with different alkyl chain lengths (C12, C16 and C22) were used. The water vapor adsorption/desorption isotherms of the core/shell particles revealed that a larger amount of water adsorbed on the core/shell particles when the pore diameter is larger. The (29)Si MAS NMR spectra of the core/shell particles showed that the amount of surface silanol groups was independent of the water vapor adsorption capacity of the products. The possible molecular recognitive photocatalysis on the products was investigated under UV irradiation using two kinds of aqueous mixtures containing different organic compounds with varied sizes and functional groups: a 4-butylphenol, 4-hexylphenol, and 4-nonylphenol mixture and a 2-nitrophenol, 2-nitro-4-phenylphenol, and 4-nitro-2,6-diphenylphenol mixture. It was found that the core/shell particles exhibited selective adsorption-driven molecular recognitive photocatalytic decomposition of 4-nonylphenol and 2-nitrophenol in the two mixtures. 相似文献
717.
Kotaro Ono 《Journal of statistical physics》2011,142(1):43-57
Within the canonical formalism, we consider a polydisperse lattice-gas model and a polydisperse continuous system interacting
with the Kac potential. We obtain rigorous expressions for free energy densities. We also exhibit phase diagrams of the bidisperse
lattice-gas model. 相似文献
718.
Low-intensity pulsed ultrasound (LIPUS) is an established therapy for fracture repair and has been used widely in the clinics, but its underlying mechanism of action remains unclear. The aim of the current research was to determine the effect of LIPUS on gap junctional cell-to-cell intercellular communication in rat bone marrow stromal cells (BMSC) in vitro and to determine whether the ability of BMSCs to communicate by gap junctions would affect their response to LIPUS. Single or daily-multiple LIPUS treatment at 1.5 MHz, 30 mW/cm2, for 20 min was applied to BMSC. We demonstrated that BMSC form functional gap junctions and single LIPUS treatment significantly increased the intracellular dye transfer between BMSC. In addition, activated phosphorylation of ERK1/2 and p38 by LIPUS stimulation was diminished when cells were treated with a gap junction inhibitor 18β-glycyrrhetinic acid (18β). We further demonstrated that 18β diminished the significant increase in alkaline phosphatase activity following LIPUS stimulation. These results suggest a potential role of gap junctional cell-to-cell intercellular communication on the effects of LIPUS in BMSC. 相似文献
719.
Dr. Shabbir Muhammad Kotaro Fukuda Takuya Minami Dr. Ryohei Kishi Dr. Yasuteru Shigeta Dr. Masayoshi Nakano 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(5):1677-1685
To reveal new structure–property relationships in the nonlinear optical (NLO) properties of fullerenes that are associated with their open‐shell character, we investigated the interplay between the diradical character (yi) and second hyperpolarizability (longitudinal component, γzzzz) in several fullerenes, including C20 , C26 , C30 , C36 , C40 , C42 , C48 , C60 , and C70 , by using the broken‐symmetry density functional theory (DFT; LC‐UBLYP (μ=0.33)/6‐31G*//UB3LYP/6‐31G*). We found that the large differences between the geometry and topology of fullerenes have a significant effect on the diradical character of each fullerene. On the basis of their different diradical character, these fullerenes were categorized into three groups, that is, closed‐shell (yi=0), intermediate open‐shell (0<yi<1), and almost pure open‐shell compounds (yi?1), which originated from their diverse topological features, as explained by odd‐electron‐density and spin‐density diagrams. For example, we found that closed‐shell fullerenes include C20 , C60 , and C70 , whereas fullerenes C26 and C36 and C30 , C40 , C42 , and C48 are pure and intermediate open‐shell compounds, respectively. Interestingly, the γzzzz enhancement ratios between C30 / C36 and C40 / C60 are 4.42 and 11.75, respectively, regardless of the smaller π‐conjugation size in C30 and C40 than in C36 and C60 . Larger γzzzz values were obtained for other fullerenes that had intermediate diradical character, in accordance with our previous valence configuration interaction (VCI) results for the two‐site diradical model. The γzzzz density analysis shows that the large positive contributions originate from the large γzzzz density distributions on the right‐ and left‐extended edges of the fullerenes, between which significant spin polarizations (related to their intermediate diradical character) appear within the spin‐unrestricted DFT level of theory. 相似文献
720.
A preparation method for Cd‐containing brown rice grains as calibration standards was developed for X‐ray fluorescence (XRF) analysis of Cd in rice grains. Calibration standards were prepared by adding 10 g of base rice grains (from Japan) to 100 ml of methanol containing 5?100 µg of Cd. The mixture was heated, cooled, and stored in a silica gel desiccator. Seven grams of each calibration standard was packed into a polyethylene cup (32‐mm internal diameter and 23‐mm height) covered with a 6‐µm‐thick polypropylene film and then subjected to XRF analysis. The calibration curves of Cd in brown and white rice grains showed good linearity in 0.50?10 mg kg?1. The detection limits of Cd in brown and white rice grains were 0.14 and 0.12 mg kg?1, respectively. The slopes of the calibration curves for Cd in brown and white rice grains were slightly different owing to absorption effects. The absorption effects were corrected using the ratio of the intensity of Cd Kα to that of Rh Kα‐Compton scattering. After correction, the calibration curves of Cd in brown and white rice grains showed identical slopes. The spike test for 5 mg kg?1 of Cd in white rice grains (from Thailand), using the corrected calibration curves, showed quantitative recoveries (92?97%). Copyright © 2013 John Wiley & Sons, Ltd. 相似文献