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71.
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
72.
Wan-Feng Zhang Xiao-Ping Xia Takahashi Eiichi Li Li Qing Yang Yan-Qiang Zhang Ya-Nan Yang Ming-Liang Liu Chunkit Lai 《Surface and interface analysis : SIA》2020,52(5):224-233
Secondary ion mass spectrometry (SIMS) has a wide range of applications in Earth Science research, thanks to its high precision and sensitivity, and its capacity in direct insitu micromeasurement. The technique is operated in ultra-high vacuum (UHV) conditions, especially for the measurement of volatiles such as hydrogen, or the water content in nominally anhydrous minerals (NAMs). To minimize the water background and obtain accurate and precise water contents in NAMs (eg, olivine) critical parameters such as presputtering time, field aperture (FA), dynamic transfer on/off, and primary beam current intensity were investigated for a CAMECA IMS 1280-HR system. When the chamber vacuum reaches approximately 2 × 10−9 mbar, we set the DTOS OFF, raster size to 50 μm and primary beam current to 5 nA, and used 2000 μm FA and 170-second presputtering time. Consequently, an approximately 1.2 ppmw water background and 3.6 ppmw limit of detection (LOD) were yielded, from analyzing the San Carlos olivine. Meanwhile, the water content and homogeneity of a range of olivine minerals were characterized for potential use as reference materials for SIMS water content measurement. Olivine water content calibration curve was also established by comparing the Fourier transform infrared (FTIR) results with the SIMS-measured 16O1H−/16O− ratios. Accuracy and precision of water content measurement were estimated to be better than approximately 10% in this study. 相似文献
73.
Total synthesis of ecteinascidin 743 总被引:1,自引:0,他引:1
Endo A Yanagisawa A Abe M Tohma S Kan T Fukuyama T 《Journal of the American Chemical Society》2002,124(23):6552-6554
The total synthesis of ecteinascidin 743 (1), an extremely potent antitumor agent, has been accomplished. The synthesis features Ugi's 4CC reaction, intramolecular Heck reaction, phenol-aldehyde cyclization, and acid-induced intramolecular sulfide formation. 相似文献
74.
Regen SL Janout V Stedronsky ER Zhang Lh Blum JS Boyajian AR Butow ME Carbonelli KL Liebentritt S Rouse RK Shay DT Vincent GA Warholic HM Yanagisawa H 《Organic letters》2000,2(14):2157-2160
The use of partially quaternized, chloromethylated polystyrene as a covalent scavenger of cholate ion in aqueous media has been demonstrated. The ability of such polymers to scavenge organic anions by covalent as well as by ionic means has important implications in the areas of medicinal and environmental chemistry, which are briefly discussed. 相似文献
75.
Yanagisawa A Kageyama H Nakatsuka Y Asakawa K Matsumoto Y Yamamoto H 《Angewandte Chemie (International ed. in English)》1999,38(24):3701-3703
Catalytic asymmetric allylation of aldehydes with allylic trimethoxysilanes was achieved with the p-Tol-BINAP small middle dotAgF complex as catalyst [Eq. (a); p-Tol-BINAP=2,2'-bis(di-p-tolylphosphanyl)-1,1'-binaphthyl)]. High anti and enantioselectivities were obtained in the reaction with crotyltrimethoxysilane, irrespective of the configuration at the double bond. 相似文献
76.
Eiichi Hanamura 《Solid State Communications》1973,12(9):951-953
The direct excitation of excitonic molecule due to the two-photon absorption process is shown to be strongly enhanced because of two effects of the resonance and the giant oscillator strength as known for the bound exciton. Then it is pointed out that the existence of the excitonic molecule can be confirmed also by this two-photon absorption spectroscopy. We discuss also the property of the excitonic molecules highly excited by this method. 相似文献
77.
Shigeo Shionoya Hiroshi Saito Eiichi Hanamura Okikazu Akimoto 《Solid State Communications》1973,12(3):223-226
Luminescence lines due to excitonic molecules are observed in CdS and CdSe. The line shape is analyzed by taking account of the broadening due to elastic collision. It is pointed out that the anisotropy of the effective hole masses makes the molecular binding energies much larger than evaluated by using the geometrical means of the hole masses. 相似文献
78.
A Reformatsky-type aldol reaction of alpha-chloroketones with aldehydes has been achieved using reactive barium as a low-valent metal in THF; this one-pot process is more effective for obtaining the desired beta-hydroxy ketones in high yields than the stepwise process in which barium enolates are prepared prior to the reaction with aldehydes. 相似文献
79.
Luminescence channels of manganese-doped spinel 总被引:1,自引:0,他引:1
Ayana Tomita Kensuke Tanaka Masanobu Shirai Kouichirou Tanaka Eiichi Hanamura 《Journal of luminescence》2004,109(1):19-24
Two independent luminescence channels are observed from manganese-doped spinel Mn:MgAl2O4. The luminescence around 520 nm is assigned to transition from the lowest electronic excited state 4T1 to the ground state 6A1 of Mn2+ (3d)5 ion by analyzing the excitation spectrum and electron spin resonance measurement. The emission at 650 nm is triggered by the band edge excitation and is assigned similarly to the charge-transfer process associated with the manganese ion. 相似文献
80.
Matsuo Y Tahara K Sawamura M Nakamura E 《Journal of the American Chemical Society》2004,126(28):8725-8734
Selective penta-addition of a methylcopper reagent followed by addition of a phenylcopper reagent to a suitably modified synthetic intermediate results in creation of 40pi-electron systems-hoop- and bowl-shaped cyclic benzenoid compounds, [10]cyclophenacene, and dibenzo-fused corannulene derivatives. The 40pi-electron cyclophenacene derivatives have been found to be chemically stable, yellow-colored, luminescent (560 nm), and EPR-silent. X-ray crystallographic analysis provided precision structural data sets. The dibenzo-fused corannulene derivatives exhibit blue-green (460 nm) to red (649 nm) fluorescence. 相似文献