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71.
High enantioselectivity in rhodium-catalyzed allylic alkylation of 1-substituted 2-propenyl acetates
[reaction: see text] Rhodium-catalyzed asymmetric allylic alkylation of 1-substituted 2-propenyl acetates with dimethyl malonate proceeded with high enantioselectivity in the presence of cesium carbonate as a base and a rhodium catalyst generated from Rh(dpm)(C(2)H(4))(2) (dpm = dipivaloylmethanato) and a chiral phosphino-oxazoline whose basic skeleton is axially chiral binaphthyl to give branch alkylation products in greater than 90% ee. 相似文献
72.
N Teno K Wanaka Y Okada Y Tsuda U Okamoto A Hijikata-Okunomiya T Naito S Okamoto 《Chemical & pharmaceutical bulletin》1991,39(11):2930-2936
Specific plasma kallikrein inhibitors were designed and synthesized and their structure-activity relationship was studied. trans-4-Aminomethylcyclohexanecarbonyl (Tra)-lysyl-4-ethoxycarbonylanilide inhibited plasma kallikrein and plasmin with IC50 values of 23 and 210 microM, respectively, indicating that this compound is fairly specific to plasma kallikrein. Tra-arginyl-4-ethoxycarbonylanilide inhibited plasma kallikrein and plasmin with IC50 values of 16 and 480 microM, respectively. Tra-homoarginyl-4-carboxyanilide inhibited plasma kallikrein and plasmin with IC50 values of 14 microM and 1 mM, respectively. Finally, Tra-Arg(Mts)-4-acetylanilide (ACA) exhibited potent and selective inhibitory activity against plasma kallikrein (IC50 value for plasma kallikrein: 2 microM and for plasmin: 42 microM). 相似文献
73.
Yoshida N Ishizuka T Yofu K Murakami M Miyasaki H Okada T Nagata Y Itaya A Cho HS Kim D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(12):2854-2866
A series of zinc(II) porphyrin-imide dyads (ZP-Im), in which an electron donating ZP moiety is directly connected to an electron accepting imide moiety in the meso position, have been prepared for the examination of energy gap dependence of intramolecular electron transfer reactions with large electronic coupling. The nearly perpendicular conformation of the imide moiety towards the porphyrin plane has been revealed by Xray crystal structures. The energy gap for charge separation, 1ZP* - Im --> ZP+ - Im-, is varied by changing the electron accepting imide moiety to cover a range of about 0.8 eV in DMF. Definitive evidence for electron transfer has been obtained in three solvents (toluene, THF, and DMF) through picosecond-femtosecond transient absorption studies, which have allowed us to determine the rates of photoinduced charge separation, 1ZP* - Im --> ZP+ - Im-, and subsequent thermal charge recombination ZP+ - Im- --> ZP - Im. The free-energy gap dependence (energy gap law) has been probed from the normal to the nearly top region for the charge separation rate alone, and only the inverted region for the charge recombination rate. Although both of the energy gap dependencies can be approximately reproduced by means of the simplified semiclassical equation, when we take into consideration the effect of the high frequency vibrations replaced by one mode of averaged frequency, many features, including the effects of solvent polarity and the electron tunneling matrix element on the energy gap law, differ considerably from those of the previously studied porphyrin-quinone systems, which have weaker interchromophore electronic interactions. 相似文献
74.
The monomeric ν(N—H) vibrations of various trisubstituted ureas of the R2UPh type and -thioureas of the R2TUPh type have been studied. The trans—out isomerism in the former and the trans—out—cis isomerism in the latter are discussed from the point of view of steric effect. The monomeric ν(N—H) vibrations of RPhUPh and RPhTUPh are also examined. The single band appearing in the spectrum of both ureas is characteristic of the cis form; this suggests the existence of phenyl—phenyl interaction (the stacking interaction proposed by Galabov et al. [10]). Behavior of ν(N—H) vibrations at several concentrations is shown to be clearly different in the three forms (trans, out and cis). The presence of the cis form is confirmed by solvent effect experiments. 相似文献
75.
Homoleptic cyclometalated iridium complexes with highly efficient red phosphorescence and application to organic light-emitting diode 总被引:7,自引:0,他引:7
Tsuboyama A Iwawaki H Furugori M Mukaide T Kamatani J Igawa S Moriyama T Miura S Takiguchi T Okada S Hoshino M Ueno K 《Journal of the American Chemical Society》2003,125(42):12971-12979
Phosphorescence studies of a series of facial homoleptic cyclometalated iridium(III) complexes have been carried out. The complexes studied have the general structure Ir(III)(C-N)(3), where (C-N) is a monoanionic cyclometalating ligand: 2-(5-methylthiophen-2-yl)pyridinato, 2-(thiophen-2-yl)-5-trifluoromethylpyridinato, 2,5-di(thiophen-2-yl)pyridinato, 2,5-di(5-methylthiophen-2-yl)pyridinato, 2-(benzo[b]thiophen-2-yl)pyridinato, 2-(9,9-dimethyl-9H-fluoren-2-yl)pyridinato, 1-phenylisoquinolinato, 1-(thiophen-2-yl)isoquinolinato, or 1-(9,9-dimethyl-9H-fluoren-2-yl)isoquinolinato. Luminescence properties of all the complexes at 298 K in toluene are as follows: quantum yields of phosphorescence Phi(p) = 0.08-0.29, emission peaks lambda(max) = 558-652 nm, and emission lifetimes tau = 0.74-4.7 micros. Bathochromic shifts of the Ir(thpy)(3) family [the complexes with 2-(thiophen-2-yl)pyridine derivatives] are observed by introducing appropriate substituents, e.g., methyl, trifluoromethyl, or thiophen-2-yl. However, Phi(p) of the red emissive complexes (lambda(max) > 600 nm) becomes small, caused by a significant decrease of the radiative rate constant, k(r). In contrast, the complexes with the 1-arylisoquinoline ligands are found to have marked red shifts of lambda(max) and very high Phi(p) (0.19-0.26). These complexes are found to possess dominantly (3)MLCT (metal-to-ligand charge transfer) excited states and have k(r) values approximately 1 order of magnitude larger than those of the Ir(thpy)(3) family. An organic light-emitting diode (OLED) device that uses Ir(1-phenylisoquinolinato)(3) as a phosphorescent dopant produces very high efficiency (external quantum efficiency eta(ex) = 10.3% and power efficiency 8.0 lm/W at 100 cd/m(2)) and pure-red emission with 1931 CIE (Commission Internationale de L'Eclairage) chromaticity coordinates (x = 0.68, y = 0.32). 相似文献
76.
Itaru Yamashita Youhei Kawabata Tadashi Kato Masakatsu Hato Hiroyuki Minamikawa 《Colloids and surfaces. A, Physicochemical and engineering aspects》2004,250(1-3):485-490
Small angle X-ray scattering (SAXS) is measured for the lamellar phase in aqueous systems of 1-o-β-3,7-dimethyoctyl-D-glucopyranoside (β-Glc(Ger)), which has recently been prepared by us, 1-o-β-decyl-D-glucopyranoside (β-GlcC10), and 1-o-β-octyl-D-glucopyranoside (β-GlcC8). The repeat distance d obtained from the position of the diffraction peak does not follow the swelling law d = 2δhc/hc, where δhc and hc are the thickness and the volume fraction of the hydrophobic layer, respectively. This may result from the fact that δhc increases and, equivalently, the surface area per surfactant molecule (as) decreases with increasing concentration. So we calculate δhc and as from the observed d value at each concentration using the above swelling law. The half-thickness δhc increases in the order β-GlcC8 < β-Glc(Ger) < β-GlcC10 at a fixed concentration. On the other hand, the data on as for β-GlcC10 and β-GlcC8 lie on the same line and the data for β-Glc(Ger) lies above this line. These results suggest that the cross-sectional area of the geranyl chain is larger than that of the glucose headgroup. Existence of water filled defects in bilayer sheets is also discussed based on the SAXS pattern and the concentration dependence of d. 相似文献
77.
Takeo Kawashiro Fumihiro Yamasawa Yasumasa Okada Hirosuke Kobayashi Kunio Tanabe 《Mathematical Programming》1991,52(1-3):1-9
The uneven distribution of ventilation—perfusion ratios (
) in diseased lungs is the major cause of arterial hypoxemia. Farhi and Yokoyama (1967) and Yokoyama and Farhi (1967) were the first who used physiologically inert gases as indicator gases to assess the uneven distribution of
Wagner and his coworkers in San Diego (1977b) extended the method and elaborated the multiple inert gas elimination technique in which blood flows in 50 compartments with different
were estimated based on data for 6 indicator gases. They analyzed the indicator gas data through an enforced smoothing technique with the ridge regression. To get smooth distributions, they introduced a weighting function for
compartments and an additional treatment for the non-negativity of the blood flow. The weighting function was empirically obtained. We analyzed the data without putting any weights on
compartments nor any additional treatment for non-negativity of blood flow. The analytical method in the present study was a modified Newton method, which is one of the enforced smoothing method. Our method was capable of recovering all distribution patterns that were found through the method reported by Wagner et al. (1977b). 相似文献
78.
79.
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