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121.
Prof. Nobutaka Fujieda Kyohei Umakoshi Yuta Ochi Dr. Yosuke Nishikawa Prof. Sachiko Yanagisawa Prof. Minoru Kubo Prof. Genji Kurisu Prof. Shinobu Itoh 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13487-13492
The dinuclear copper enzyme, tyrosinase, activates O2 to form a (μ-η2:η2-peroxido)dicopper(II) species, which hydroxylates phenols to catechols. However, the exact mechanism of phenolase reaction in the catalytic site of tyrosinase is still under debate. We herein report the near atomic resolution X-ray crystal structures of the active tyrosinases with substrate l -tyrosine. At their catalytic sites, CuA moved toward l -tyrosine (CuA1 → CuA2), whose phenol oxygen directly coordinates to CuA2, involving the movement of CuB (CuB1 → CuB2). The crystal structures and spectroscopic analyses of the dioxygen-bound tyrosinases demonstrated that the peroxide ligand rotated, spontaneously weakening its O−O bond. Thus, the copper migration induced by the substrate-binding is accompanied by rearrangement of the bound peroxide species so as to provide one of the peroxide oxygen atoms with access to the phenol substrate's ϵ carbon atom. 相似文献
122.
Mack J Bunya M Shimizu Y Uoyama H Komobuchi N Okujima T Uno H Ito S Stillman MJ Ono N Kobayashi N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(16):5001-5020
The optical spectra of a series of core-modified tetrabenzoporphyrins were analyzed to determine the effects of core modification, ligand folding, and partial benzo substitution at the ligand periphery on the electronic structure by using magnetic circular dichroism (MCD) and NMR spectroscopy, X-ray crystallography, cyclic and differential pulse voltammetry, and TD-DFT calculations. Planar 21-carba-, 21-thia-, 21,23-dithia-, and 21-oxa-23-thiatetrabenzo[b,g,l,q]porphyrins reported previously were studied together with the previously unreported 21-oxa- and 21-carba-23-thiatetrabenzo[b,g,l,q]porphyrins. The optical properties of these compounds are compared to those of tetrabenzo[b,g,l,q]-, 5,10,15,20-tetraphenyl-, 5,10,15,20-tetraphenyltetrabenzo[b,g,l,q]-21-thia-, 5,10,15,20-tetraphenyltetrabenzodithia-, 5,10,15,20-tetraphenyldibenzo[g,q]-21,23-dithia-, 5,10,15,20-tetraphenyldibenzo[b,l]-21,23-dithia-, 5,10,15,20-tetraphenyltribenzo[g,q,l]-21-thia-, and 5,10,15,20-tetraphenylbenzo[b]-21-thiaporphyrins. Michl's perimeter model and Gouterman's four-orbital model are used to conceptualize the results and to account for red shifts commonly observed in the spectral bands of nonplanar porphyrinoids. 相似文献
123.
Imahori H Fujimoto A Kang S Hotta H Yoshida K Umeyama T Matano Y Isoda S Isosomppi M Tkachenko NV Lemmetyinen H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(24):7265-7275
Novel gold nanoparticles modified with a mixed self-assembled monolayer of porphyrin alkanethiol and short-chain alkanethiol were prepared (first step) to examine the size and shape effects of surface holes (host) on porphyrin-modified gold nanoparticles. The porphyrin-modified gold nanoparticles with a size of about 10 nm incorporated C60 molecules (guest) into the large, bucket-shaped holes, leading to the formation of a supramolecular complex of porphyrin-C60 composites (second step). Large composite clusters with a size of 200-400 nm were grown from the supramolecular complex of porphyrin-C60 composites in mixed solvents (third step) and deposited electrophoretically onto nanostructured SnO2 electrodes (fourth step). Differences in the porphyrin:C60 ratio were found to affect the structures and photoelectrochemical properties of the composite clusters in mixed solvents as well as on the SnO2 electrodes. The photoelectrochemical performance of a photoelectrochemical device consisting of SnO2 electrodes modified with the porphyrin-C60 composites was enhanced relative to a reference system with small, wedged-shaped surface holes on the gold nanoparticle. Time-resolved transient absorption spectroscopy with fluorescence lifetime measurements suggest the occurrence of ultrafast electron transfer from the porphyrin excited singlet states to C60 or the formation of a partial charge-transfer state in the composite clusters of supramolecular complexes formed between porphyrin and C60 leading to efficient photocurrent generation in the system. Elucidation of the relationship between host-guest interactions and photoelectrochemical function in the present system will provide valuable information on the design of molecular devices and machines including molecular photovoltaics. 相似文献
124.
125.
Soga S Shirai H Kobori M Hirayama N 《Journal of chemical information and modeling》2008,48(8):1679-1685
The idea that there should be a specific site on a protein for a particular functional small molecule is widespread. It is, however, usually not so easy to understand what characteristics of the site determine the binding ability of the functional small molecule. We have focused on the concurrence rate of the 20 standard amino acids at such binding sites. In order to correlate the concurrence rate and the specific binding site, we have analyzed high-quality X-ray structures of complexes between proteins and small molecules. A novel index characterizing the binding site based on the concurrency rate has been introduced. Using this index we have identified that there is a specific concavity designated as a chemocavity where a specific group of small molecules, i.e., canonical molecular group, is highly inclined to be bound. This study has demonstrated that a chemocavity is reserved for a specific canonical molecular group, and the prevalent idea has been confirmed. 相似文献
126.
Huihui Li Yosuke Imai Takanori Takiue Hiroki Matsubara Makoto Aratono 《Colloid and polymer science》2014,292(5):1209-1215
The composition of the adsorbed film and the excess Gibbs energy of adsorption $ {\widehat{g}}^{\mathrm{H},\mathrm{E}} $ were evaluated from thermodynamic analysis of surface tensions for the 1-decyl-3-methylimidazoulium bromide (C10mimBr)–tetraethylene glycol monooctyl ether (C8E4) and 1-decyl-3-methyl-imidazolium tetrafluorobrorate (C10mimBF4)–C8E4 systems, where the counter anion of imidazolium salts is different from each other. The higher miscibility of two components compared to an ideal mixing and thus negative $ {\widehat{g}}^{\mathrm{H},\mathrm{E}} $ were observed in the former, which comes from the ion–dipole interaction between imidazolium cation and the oxyethylene group of C8E4. On the other hand, the lower miscibility and thus positive $ {\widehat{g}}^{\mathrm{H},\mathrm{E}} $ were observed for the latter. Such differences were attributed to that BF4 ? forms two hydrogen bonds and has stronger affinity with the cationic head group of C10mim+ than Br?. This results in that the ion–dipole interaction between C8E4 and C10mim+ cation is diminished in the C10mimBF4–C8E4 system. 相似文献
127.
High‐performance liquid chromatography separation of unsaturated organic compounds by a monolithic silica column embedded with silver nanoparticles
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Yang Zhu Kei Morisato George Hasegawa Nirmalya Moitra Tsutomu Kiyomura Hiroki Kurata Kazuyoshi Kanamori Kazuki Nakanishi 《Journal of separation science》2015,38(16):2841-2847
The optimization of a porous structure to ensure good separation performances is always a significant issue in high‐performance liquid chromatography column design. Recently we reported the homogeneous embedment of Ag nanoparticles in periodic mesoporous silica monolith and the application of such Ag nanoparticles embedded silica monolith for the high‐performance liquid chromatography separation of polyaromatic hydrocarbons. However, the separation performance remains to be improved and the retention mechanism as compared with the Ag ion high‐performance liquid chromatography technique still needs to be clarified. In this research, Ag nanoparticles were introduced into a macro/mesoporous silica monolith with optimized pore parameters for high‐performance liquid chromatography separations. Baseline separation of benzene, naphthalene, anthracene, and pyrene was achieved with the theoretical plate number for analyte naphthalene as 36 000 m?1. Its separation function was further extended to cis/trans isomers of aromatic compounds where cis/trans stilbenes were chosen as a benchmark. Good separation of cis/trans‐stilbene with separation factor as 7 and theoretical plate number as 76 000 m?1 for cis‐stilbene was obtained. The trans isomer, however, is retained more strongly, which contradicts the long‐ established retention rule of Ag ion chromatography. Such behavior of Ag nanoparticles embedded in a silica column can be attributed to the differences in the molecular geometric configuration of cis/trans stilbenes. 相似文献
128.
Tanaka H Zaima N Yamamoto N Suzuki M Mano Y Konno H Unno N Setou M 《Analytical and bioanalytical chemistry》2011,400(7):1873-1880
Arteriovenous fistulae (AVF) using vein grafts are frequently used for vascular access in hemodialysis. When superficial veins
are used as autogenous access grafts for hemodialysis, atherosclerotic-like tissue degeneration often causes stenosis and
obstruction. Although the differences between the pathology of degeneration in AVF and atherosclerosis (i.e., peripheral artery
occlusive disease (PAD)) are known, their underlying molecular mechanisms are not. We determined the characteristic abnormal
lipid metabolism of AVF. Oil red O staining clearly showed the accumulation of lipid molecules in AVF and PAD tissues. We
found that the staining pattern was different between AVF and PAD tissues. The media and adventitia of AVF and the intima
and media of PAD were intensely stained. Quantitative lipid analysis revealed that the amount of PL was significantly increased
in AVF and PAD. Next, we performed matrix-assisted laser desorption/ionization imaging mass spectroscopy and determined the
characteristic distribution of lysophosphatidylcholine (LPC) and phosphatidylcholine (PC) in AVF. The distribution patterns
of LPC (1-acyl 16:0) and PC (diacyl 16:0/20:4) were consistent with the Oil red O staining images, suggesting that metabolisms
related to LPC (1-acyl 16:0) and PC (diacyl 16:0/20:4) are altered in AVF. 相似文献
129.
130.
[reaction: see text]. Stereocontrolled synthesis of the ABC ring framework of zoanthenol has been achieved. Our studies show that a beta,beta-disubstituted enone can act as a good acceptor of arylpalladium intermediates in the formation of a congested benzylic quaternary carbon center through an intramoleculer Mizoroki-Heck reaction. The cis B/C ring system was stereoselectively converted to the trans-fused framework through a SmI2-promoted deoxygenation of the alpha-hydroxy ketone. 相似文献