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51.
Takashi Tokoroyama Masamitsu Tsukamoto Toshihiro Asada Hideo Iio 《Tetrahedron letters》1987,28(52):6645-6648
Doubly stereocontrolled cyclization of the allylsilane derivative 1 followed by trapping of the enolate with ClCH2SMe gives in one-pot manner the decalone derivatve 5 in which all of the four contiguous diastereomeric centers of
-clerodane skeleton have been secured. The total synthesis of linaridial 4 have been accomplished from 5. 相似文献
52.
Ekenechukwu C. Okafor Masaaki Tsukamoto Akihiro Hayakawa K.D. Kunkuma A. Somarathne Taku Kudo Taku Tsujimura Hideaki Kobayashi 《Proceedings of the Combustion Institute》2021,38(4):5139-5146
The influence of wall heat loss on the emission characteristics of ammonia-air swirling flames has been investigated employing Planar Laser-Induced Fluorescence imaging of OH radicals and Fourier Transform Infrared spectrometry of the exhaust gases in combustors with insulated and uninsulated walls over a range of equivalence ratios, ?, and pressures up to 0.5 MPa. Strong influence of wall heat loss on the flames led to quenching of the flame front near the combustor wall at 0.1 MPa, resulting in large unburned NH3 emissions, and inhibited the stabilization of flames in the outer recirculating zone (ORZ). A decrease in heat loss effects with an increase in pressure promoted extension of the fuel-rich stabilization limit owing to increased recirculation of H2 from NH3 decomposition in the ORZ. The influence of wall heat loss resulted in emission trends that contradict already reported trends in literature. NO emissions were found to be substantially low while unburned NH3 and N2O emissions were high at fuel-lean conditions during single-stage combustion, with values such as 55 ppmv of NO, 580 ppmv of N2O and 4457 ppmv of NH3 at ? = 0.8. In addition, the response of the flame to wall heat loss as pressure increased was more important than the effects of pressure on fuel-NO emission, thereby leading to an increase in NO emission with pressure. It was found that a reduction in wall heat loss or a sufficiently long fluid residence time in the primary combustion zone is necessary for efficient control of NH3 and N2O emissions in two-stage rich-lean ammonia combustors, the latter being more effective for N2O in addition to NO control. This study demonstrates that the influence of wall heat loss should not be ignored in emissions measurements in NH3-air combustion, and also advances the understanding of previous studies on ammonia micro gas turbines. 相似文献
53.
Evaluation of chemiluminescence reagents for selective detection of reactive oxygen species 总被引:2,自引:0,他引:2
Shinya Yamaguchi Kaname Ohyama Maiko Kohno Akira Takadate Naotaka Kuroda 《Analytica chimica acta》2010,665(1):74-27
In order to evaluate the chemiluminescence (CL) reagents for selective detection of reactive oxygen species (ROS), we comprehensively measured the CL responses of 20 CL reagents (three luminol derivatives, two imidazopyrazinone derivatives, eight lophine derivatives, six acridinium ester derivatives and lucigenin) against six types of ROS (superoxide anion: O2−, hydroxyl radical: OH, hydrogen peroxide: H2O2, hypochlorite anion: ClO−, singlet oxygen: 1O2, and nitric oxide: NO). As a result of the screening, it was found that nine CL reagents selectively detected O2− while one CL reagent selectively detected OH. However, no CL reagent had selectivity on the detection of H2O2, ClO−, 1O2 and NO. Our screening results could help to select the most suitable CL reagent for selective determination of different ROS.As an application study, 4-methoxyphenyl-10-methylacridinium-9-carboxylate (MMAC), one of the acridinium ester derivatives, showed high selectivity on the detection of O2−, and thus was applied to the assay of superoxide dismutase (SOD) activity. The dynamic range and detection limit of the developed CL assay were 0.1-10 and 0.06 U mL−1, respectively. Significant correlation (r = 0.997) was observed between the results by the CL assay using MMAC and the spectrophotometric assay using 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-(2,4-disulfophenyl)-2H-tetrazolium monosodium salt. 相似文献
54.
o-Ethynylbenzyl phenyl selenides regioselectively reacted with trifluoromethanesulfonic acid to afford the (Z)-1-methylidene-2-phenyl-1,3-dihydro-1H-benzo[c]selenophenium salts as the major products during the 5-exo-dig mode cyclization in good yields together with minor E isomers. The structure of the major (Z)-selenophenium salt was established by the single crystal X-ray crystallographic analysis using a tert-butyl derivative. 相似文献
55.
K Imai A Nishitani Y Tsukamoto W H Wang S Kanda K Hayakawa M Miyazaki 《Biomedical chromatography : BMC》1990,4(3):100-104
The catalytic effect of bases (imidazole, pyridine, Tris and triethylamine) on the peroxyoxalate chemiluminescence (PO-CL) reaction for high performance liquid chromatography (HPLC) was investigated. Imidazole increased PO-CL intensity extraordinarily, whereas the other bases (pyridine, Tris and triethylamine) did not. The peak heights of dipyridamole (coronary vasodilator) obtained using the eluents containing buffers were largest at pH 7.0, a few times less at pH 6.0 and pH 5.0, 100 times less at pH 4.0 and a few hundred times less at pH 3.0. The eluents containing buffers at pH 3, 4, 5, 6 or 7 each with imidazole increased the peak heights by a few to ten times as compared with those without imidazole, and those peak heights were within one order of magnitude. On the other hand, the eluent containing buffer at pH 2 did not affect the peak heights with or without imidazole. Bis(4-nitro-2-(3,6,9-trioxadecyloxycarbonyl)phenyl) oxalate (TDPO) alone and bis(2,4-dinitrophenyl)oxalate (DNPO) plus TDPO were recommended to be used against eluents containing buffers of pH 5-7 and pH 3-4, respectively. Dipyridamole and benzydamine hydrochloride (anti-inflammatory drug) were separated on the ODS column and detected by the present system. The detection limits of dipyridamole and benzydamine hydrochloride were 40 amol and 270 fmol, respectively. 相似文献
56.
K. Imai S. Higashidate A. Nishitani Y. Tsukamoto M. Ishibashi J. Shoda T. Osuga 《Analytica chimica acta》1989
Oxo-steroids and oxo-bile acid ethyl esters were derivatized with 5-N,N-dimethylamino-naphthalene-1-sulphonohydrazide (DNS-hydrazine) to DNS-hydrazone in the presence of hydrochloric acid in ethanol or trifluoroacetic acid in benzene, purified by high-performance gel-permeation chromatography, separated on an ODS column with an eluent containing tetrahydrofuran and detected via a peroxyoxalate chemiluminescence reaction using bis[4-nitro-2-(3,6,9-trioxadecyloxycarbonyl)phenyl] oxalate (TDPO). Sensitive detection (femtomole level) of each oxo-steroid which appeared as a single peak was achieved. The procedure for the isolation of oxo-bile acids developed for GC-MS allowed the detection by this system of an unusual oxo-bile acid, 7α-hydroxy-3-oxo-5β-cholanic acid, at the nanomole l?1 level in urine from a patient with cholestatic liver disease. 相似文献
57.
Koki Tsukamoto Toshio Watanabe Umpei Nagashima Yutaka Akiyama 《Journal of Molecular Structure》2005,732(1-3):87-98
A reaction mechanism of a nitric oxide reductase, cytochrome P450nor (P450nor) from Fusarium oxysporum, was clarified by using Density functional theory and Hartree–Fock calculations. In this reaction mechanism, molecular orbital (MO) analysis revealed that the NO ligand dissociates from the heme iron immediately after one-electron reduction by NADH, and MO energy analysis revealed that NADH acts as a one-electron reducer, not as a two-electron reducer, and that NADH has a pivotal role different from other one-electron reducers. The role of NADH is to act as a double one-electron donor (i.e. one-electron transfer occurring twice) and to combine with the NO− molecule by charge recombination reaction. Our quantum chemical calculations indicated that all reactions occurring in the heme pocket are too fast to become rate-limiting. Therefore, the rate-limiting steps in the proposed reaction mechanism are the process of capturing NO and NADH into the heme pocket and the process of expelling a product generated in the heme pocket. Kinetics of these processes was discussed based on large-amplitude vibration, which helps capturing and expelling processes in a widely opened heme pocket of P450nor. The reaction mechanism proposed here well explains published experimental data. 相似文献
58.
59.
Vitamin K is a fat-soluble vitamin involved in blood coagulation and bone metabolism. The detection and monitoring of vitamin K homologues in rheumatoid arthritis (RA) patients is a challenging problem due to the smaller concentrations of vitamin K and the presence of several interfering medications. Therefore, this study aimed to develop a new highly sensitive and selective chemiluminescence (CL) method designated to quantify vitamin K homologues in plasma of RA patients including phylloquinone (PK, vitamin K1), menaquinone-4 (MK-4, vitamin K2) and menaquinone-7 (MK-7, vitamin K2). The method was based on the unique photochemical properties of vitamin K homologues that were exploited for selective luminol CL reaction. The correlation coefficients of 0.998 or more were obtained in the concentration ranges of 0.1-100 ng mL−1 vitamin K homologues. The detection limits were 0.03-0.1 ng mL−1 in human plasma for vitamin K homologues. The developed HPLC-CL system was successfully applied for selective determination of vitamin K homologues in plasma of RA patients. The developed method may provide a useful tool for monitoring vitamin K homologues in different clinical studies such as RA, osteoporosis and hepatocellular carcinoma in which vitamin K is intervented. 相似文献
60.
Tsukamoto D Ikeda M Shiraishi Y Hara T Ichikuni N Tanaka S Hirai T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(35):9816-9824
Semiconductor TiO2 particles loaded with WO3 (WO3/TiO2), synthesized by impregnation of tungstic acid followed by calcination, were used for photocatalytic oxidation of alcohols in water with molecular oxygen under irradiation at λ>350 nm. The WO3/TiO2 catalysts promote selective oxidation of alcohols to aldehydes and show higher catalytic activity than pure TiO2. In particular, a catalyst loading 7.6 wt % WO3 led to higher aldehyde selectivity than previously reported photocatalytic systems. The high aldehyde selectivity arises because subsequent photocatalytic decomposition of the formed aldehyde is suppressed on the catalyst. The TiO2 surface of the catalyst, which is active for oxidation, is partially coated by the WO3 layer, which leads to a decrease in the amount of formed aldehyde adsorbed on the TiO2 surface. This suppresses subsequent decomposition of the aldehyde on the TiO2 surface and results in high aldehyde selectivity. The WO3/TiO2 catalyst can selectively oxidize various aromatic alcohols and is reusable without loss of catalytic activity or selectivity. 相似文献