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21.
Horio T Yamazaki M Maeda S Hatamoto T Kishimoto N Ohno K 《The Journal of chemical physics》2005,123(19):194308
A low-temperature discharge nozzle source with a liquid-N(2) circulator for He*(2(3)S) metastable atoms has been developed in order to obtain the state-resolved collision energy dependence of Penning ionization cross sections in a low collision energy range from 20 to 80 meV. By controlling the discharge condition, we have made it possible to measure the collision energy dependence of partial ionization cross sections (CEDPICS) for a well-studied system of CH(3)CN+He*(2(3)S) in a wide energy range from 20 to 350 meV. The anisotropic interaction potential energy surface for the present system was obtained starting from an ab initio model potential via an optimization procedure based on classical trajectory calculations for the observed CEDPICS. A dominant attractive well depth was found to be 423 meV (ca. 10 kcal/mol) at a distance of 3.20 A from the center of mass of CH(3)CN in the N-atom side along the CCN axis. In addition, a weak attractive well (ca. 0.9 kcal/mol) surrounding the methyl group (-CH(3)) has been found and ascribed to the interaction between an unoccupied molecular orbital of CH(3)CN and 2s atomic orbital of He*(2(3)S). 相似文献
22.
Wang CR Kai T Tomiyama T Yoshida T Kobayashi Y Nishibori E Takata M Sakata M Shinohara H 《Angewandte Chemie (International ed. in English)》2001,40(2):265
The cover picture shows a section of the electron charge density of the first metal carbide endohedral metallofullerene (Sc(2)C(2))@C(84) obtained from a synchrotron X-ray powder diffraction study by the maximum entropy method (MEM). The several density maxima, which correspond to scandium and carbon atoms, are clearly seen inside the C(84) carbon cage. The MEM charge density distribution also reveals that the C(84) cage has D(2d) symmetry (no. 23) and that the C(2) axis is parallel to the <100> face-centered cubic (fcc) direction of the unit cell. As a consequence of the site symmetry being 4mm, the C(2) axis of (Sc(2)C(2))@C(84) is oriented to six equivalent <100> directions and shows a merohedral disorder. The resultant Sc small middle dot small middle dot small middle dotSc distances and C-C bond lengths of the Sc(2)C(2) cluster are 0.429(2) and 0.142(6) nm, respectively. The observed C-C bond length is between that of a typical single and a double bond, and is very close to that of the C-C bond (0.143 nm) combining two pentagons in a C(60) molecule. More about this fascinating structure can be found in the contribution by Shinohara and co-workers on p. 397 ff. 相似文献
23.
Torizawa T Ono AM Terauchi T Kainosho M 《Journal of the American Chemical Society》2005,127(36):12620-12626
The unambiguous assignment of the aromatic ring resonances in proteins has been severely hampered by the inherently poor sensitivities of the currently available methodologies developed for uniformly 13C/15N-labeled proteins. Especially, the small chemical shift differences between aromatic ring carbons and protons for phenylalanine residues in proteins have prevented the selective observation and unambiguous assignment of each signal. We have solved all of the difficulties due to the tightly coupled spin systems by preparing regio-/stereoselectively 13C/2H/15N-labeled phenylalanine (Phe) and tyrosine (Tyr) to avoid the presence of directly connected 13C-1H pairs in the aromatic rings. The superiority of the new labeling schemes for the assignment of aromatic ring signals is clearly demonstrated for a 17 kDa calcium binding protein, calmodulin. 相似文献
24.
Sekino E Kumamoto T Tanaka T Ikeda T Ishikawa T 《The Journal of organic chemistry》2004,69(8):2760-2767
(-)-Quinine-catalyzed intramolecular oxo-Michael addition (IMA) of 7-hydroxy-5-methoxy-8-tigloylcoumarins was developed for the enantioselective construction of 2,3-dimethyl-4-chromanone systems in the context of the asymmetric synthesis of anti-HIV-1 active Calophyllum coumarins. Combination of the IMA and MgI(2)-assisted demethylation of the 5-methoxy group along with isomerization of the formed chromanone systems as key steps successfully led to the concise synthesis of (+)-inophyllum B and (+)-calanolide A, possible candidates for AIDS drugs. Further examination of the asymmetric IMA with cinchona alkaloids lacking a methoxy group on the quinoline skeleton suggested the influence of the methoxy substituent on stereoselectivity at the stereogenic centers of the chromanone systems. 相似文献
25.
Iida T Satoh H Maeda K Yamamoto Y Asakawa K Sawada N Wada T Kadowaki C Itoh T Mase T Weissman SA Tschaen D Krska S Volante RP 《The Journal of organic chemistry》2005,70(23):9222-9229
[Reaction: see text]. The synthesis of neuropeptide Y antagonist 1, currently under clinical investigation for the treatment of obesity, is described. The convergent synthesis from trans-spirolactone carboxylic acid intermediate 2a and aminopyrazole 3 is predicated on a stereoselective route to the former. The coupling reaction of ethyl 4-oxocyclohexanecarboxylate (10a) with lithiated isonicotinamide 11 was investigated in detail, but even optimized conditions only provided a 45:55 ratio of trans:cis isomers (12a:12b). While selective crystallization schemes were developed to isolate the thermodynamically less stable trans isomer 2a, improved stereocontrol was subsequentially achieved by the application of ketene chemistry. The ketene formation and quench was investigated under a variety of conditions aimed at maximizing the trans:cis ratio. Reacting a mixture of carboxylic acids 2a and 2b with POCl3 in THF, followed by concomitant addition of tert-butyl alcohol in the presence of TMEDA at 35 degrees C provided a 4:1 ratio of trans:cis tert-butyl esters (18a:18b) via in situ ketene formation. Ester hydrolysis, followed by selective crystallization of undesired 2b as the HCl salt, led to isolation of 2a in 47% overall yield. Aminopyrazole intermediate 3 was synthesized via the condensation reaction of 2-fluorophenylhydrazine hydrochloride (4a) with acrylonitrile derivative 5 in 65-70% yield. Coupling of advanced intermediates 2a and 3b via activation with thionyl chloride gave a 92% yield of 1. 相似文献
26.
Atsuhisa Mimoto Sojiro Kon Takuya Motomura Minoru Inaba 《Journal of fluorine chemistry》2005,126(7):1101-1110
The Ni-based alloys, such as Ni-Co, Ni-Mn, Ni-Ag, Ni-Cu, Ni-Al and Ni-Si, prepared by hot isostatic pressing (HIP) at 1000 °C under 2 × 108 Pa for 2 h were employed as the anodes for electrolytic production of NF3. The current efficiencies for NF3 formation were 42-38, 52-40, 52-47, 63-62, 50 and 41% for Ni-Co, Ni-Mn, Ni-Ag, Ni-Cu, Ni-Al and Ni-Si alloys, respectively. The current efficiencies only on Ni-Cu alloys with Cu concentrations lower than 10 mol% were almost the same as those on Ni sheet and HIPed Ni anodes, whereas those on the other alloys used in this study were smaller compared with those on both Ni anodes. On the other hand, the current losses caused by anodic dissolution of Ni-Co, Ni-Mn, Ni-Ag, Ni-Cu, Ni-Al and Ni-Si alloy electrodes were 7.95-4.42, 6.40-7.02, 5.60-6.30, 3.34-6.33, 5.10 and 0.18%, respectively. The anode consumptions of Ni-5 mol% Cu and Ni-5 mol% Si alloys were almost the same or smaller compared with those of Ni sheet and HIPed Ni electrodes, though those of other alloys used were large compared with those of both Ni anodes. Consequently, addition of Cu to the nickel matrix is available for a cheaper cost of anode with keeping a same current efficiency as that on the Ni anode and addition of Si to the nickel matrix is effective for decreasing anode consumption largely. A Ni sheet electrode containing a trace of impurities, such as Co, Mn, Ag and Al, is also favorable as the anode for electrolytic production of NF3. 相似文献
27.
Masaki Shimizu Prof. Dr. Takuya Kurahashi Dr. Katsuhiro Shimono Dr. Kei Tanaka Ikuhiro Nagao Shin‐ichi Kiyomoto Tamejiro Hiyama Prof. Dr. 《化学:亚洲杂志》2007,2(11):1400-1408
Treatment of 1,1‐bis(pinacolatoboryl)ethene with an excess of 1‐bromo‐1‐lithioethene gave 2,3‐bis(pinacolatoboryl)‐1,3‐butadiene in high yield. Palladium‐catalyzed cross‐coupling of the resulting diborylbutadiene with aryl iodides took place smoothly in the presence of a catalytic amount of Pd(OAc)2/PPh3 and aqueous KOH to give 2,3‐diaryl‐1,3‐butadienes in good yields. The coupling reaction with commercially available 4‐acetoxyphenylmethyl chloride under the same conditions followed by hydrolysis of the acetyl groups gave anolignan B in a one‐pot manner. A variety of [3]‐ to [6]dendralenes were synthesized by palladium‐catalyzed coupling of the diene or 1,1‐bis(pinacolato)borylethene with alkenyl or dienyl halides, respectively, in good yields. 相似文献
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