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排序方式: 共有794条查询结果,搜索用时 10 毫秒
51.
A conceptually new strategy for asymmetric catalysis, namely asymmetric activation, in which a chiral activator selectively activates one enantiomer of a racemic chiral catalyst, and a highly efficient screening system for finding the most effective catalysts, namely super high throughput screening (SHTS), by which the reaction can be conducted in parallel and the ee% of the product is allowed to determine within minutes, are summarized in the present account. It is reasonable to believe that SHTS technique combined with asymmetric activation or deactivation principle will provide a very powerful methodology for finding the new catalysts and the best catalyst tuning for asymmetric reactions. 相似文献
52.
Reactions of the iridium(III) nitrosyl complex [Ir(NO)Cl2(PPh3)2] (1) with hydrosulfide and arenethiolate anions afforded the square-pyramidal iridium(III) complex [Ir(NO)(SH)2(PPh3)2] (2) with a bent nitrosyl ligand and a series of the square-planar iridium(I) complexes [Ir(NO)(SAr)2(PPh3)] (3a, Ar = C6H2Me3-2,4,6 (Mes); 3b, Ar = C6H3Me2-2,6 (Xy); 3c, Ar = C6H2Pri3-2,4,6) containing a linear nitrosyl ligand, respectively. Complex 1 also reacted with alkanethiolate anions or alkanethiols to give the thiolato-bridged diiridium complexes [Ir(NO)(mu-SPri)(SPri)(PPh3)]2 (4) and [Ir(NO)(mu-SBut)(PPh3)]2 (5). Complex 4 contains two square-pyramidal iridium(III) centers with a bent nitrosyl ligand, whereas 5 contains two tetrahedral iridium(0) centers with a linear nitrosyl ligand and has an Ir-Ir bond. Upon treatment with benzoyl chloride, 3a and 3b were converted into the (diaryl disulfide)- and thiolato-bridged dichlorodiiridium(III) complexes [[IrCl(mu-SC6HnMe4-nCH2)(PPh3)]2(mu-ArSSAr)] (6a, Ar = Mes, n = 2; 6b, Ar = Xy, n = 3) accompanied by a loss of the nitrosyl ligands and cleavage of a C-H bond in an ortho methyl group of the thiolato ligands. Similar treatment of 4 gave the dichlorodiiridium complex [Ir(NO)(PPh3)(mu-SPri)3IrCl2(PPh3)] (7), which has an octahedral dichloroiridium(III) center and a distorted trigonal-bipyramidal Ir(I) atom with a linear nitrosyl ligand. The detailed structures of 3a, 4, 5, 6a, and 7 have been determined by X-ray crystallography. 相似文献
53.
Hideo Inaba Fujio Komatsu Akihiko Horibe Naoto Haruki Akito Machida 《Heat and Mass Transfer》2008,44(11):1305-1313
This paper describes heat and mass transfer characteristics of organic sorbent coated on heat transfer surface of a fin-tube
heat exchanger. The experiments in which the moist air was passed into the heat exchanger coated with sorption material were
conducted under various conditions of air flow rate (0.5–1.0 m/s) and the temperature of brine (14–20°C) that was the heat
transfer fluid to cool the air flow in the dehumidifying process. It is found that the sorption rate of vapor is affected
by the air flow rate and the brine temperature. Meanwhile, the attempt of clarifying the sorption mechanism is also conducted.
Finally the average mass transfer coefficient of the organic sorbent coated on heat transfer surface of a fin-tube heat exchanger
is non-dimensionalzed as a function of Reynolds number and non-dimensional temperature, and it is found that the effect of
non-dimensional temperature on them is larger than Reynolds number . 相似文献
54.
Kuwamura N Kitano K Hirotsu M Nishioka T Teki Y Santo R Ichimura A Hashimoto H Wright LJ Kinoshita I 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(38):10708-10715
Interchange between the nickel +2 and +3 oxidation states precisely controls the reversible rearrangement of the tris(2-pyridylthio)methanide (tptm) ligand in the organometallic nickel(II) complex [{Ni(μ-Br)-(tptm)}(2)] (2). Oxidation of 2 first gives the corresponding Ni(III) complex [{Ni(μ-Br)(tptm)}(2)][PF(6)](2) (4). However, in solution the tptm ligand in 4 slowly undergoes a rearrangement, in which the N and S atoms of one of the pyridylthiolate arms exchange Ni and C bonding partners, thereby resulting in an "N,S-confused" isomer of tptm in the product, [NiBr(bpttpm)]PF(6) (5; bpttpm= bis(2-pyridylthio)(2-thiopyridinium)-methyl). Reduction of 5 reverses this ligand rearrangement and 2 is reformed quantitatively. The individual steps involved in these unusual ligand rearrangements were investigated by a number of methods, including voltammetric analysis, and a mechanism for this process is proposed. X-ray crystal structure determinations of the key compounds 2, 4 and 5 have been obtained. 相似文献
55.
Kakiuchi F Kan S Igi K Chatani N Murai S 《Journal of the American Chemical Society》2003,125(7):1698-1699
The ruthenium-catalyzed reaction of aromatic ketones with arylboronic acid esters (arylboronates) gave the ortho arylation product. For this coupling reaction, a RuH2(CO)(PPh3)3 complex exhibited the highest catalytic activity among the complexes screened. Several aromatic ketones, for example, acetophenones, acetonaphthone, alpha-tetralone, and benzosuberone, can be used in this coupling reaction. A variety of arylboronates containing electron-donating (OMe and NMe2) and -withdrawing (F and CF3) groups were found to react with aromatic ketones to give the corresponding aylation products. The corresponding arylboronic acids could be used in this coupling reaction, but the yields were slightly lower, as compared to those of the reaction using the corresponding arylboronates. 相似文献
56.
Rieko Furuyama Junji Saito Sei-ichi Ishii Makoto Mitani Shigekazu Matsui Yasushi Tohi Haruyuki Makio Naoto Matsukawa Hidetsugu Tanaka Terunori Fujita 《Journal of molecular catalysis. A, Chemical》2003,200(1-2):31-42
This contribution reports ethylene and propylene polymerization behavior of a series of Ti complexes bearing a pair of phenoxy–imine chelate ligands. The bis(phenoxy–imine)Ti complexes in conjunction with methylalumoxane (MAO) can be active catalysts for the polymerization of ethylene. Unexpectedly, this C2 symmetric catalyst produces syndiotactic polypropylene. 13C NMR spectroscopy has revealed that the syndiotacticity arises from a chain-end control mechanism. Substitutions on the phenoxy–imine ligands have substantial effects on both ethylene and propylene polymerization behavior of the complexes. In particular, the steric bulk of the substituent ortho to the phenoxy–oxygen is fundamental to obtaining high activity and high molecular weight for ethylene polymerization and high syndioselectivity for the chain-end controlled propylene polymerization. The highest ethylene polymerization activity, 3240 kg/mol-cat h, exhibited by a complex having a t-butyl group ortho to the phenoxy–oxygen, represents one of the highest reported to date for Ti-based non-metallocene catalysts. Additionally, the polypropylene produced exhibits a Tm, 140 °C, and syndioselectivity, rrrr 83.7% (achieved by a complex bearing a trimethylsilyl group ortho to the phenoxy–oxygen) that are among the highest for polypropylenes produced via a chain-end control mechanism. Hence, the bis(phenoxy–imine)Ti complexes are rare examples of non-metallocene catalysts that are useful for the polymerization of not only ethylene but also propylene. 相似文献
57.
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
58.
Kazuhiko Kandori Kazunao Hayashi Masaki Matsukawa Masao Fukusumi Yoshiaki Morisada 《Colloid and polymer science》2010,288(10-11):1071-1079
The shape and porosity of hematite particles, produced from a forced hydrolysis reaction of acidic FeCl3 solution, were controlled by using Pluronics as nonionic surfactants (0–4 wt.%). Pluronics possess a nominal formula of (PEO) x –(PPO) y –(PEO) x . The effect of Pluronics with low hydrophilicity (PEO contents were less than 50 mol%) was small and provided spherical particles the same as that of the system without Pluronics (control system). However, Pluronics with higher hydrophilicity (PEO contents were over 50 mol%) gave ellipsoidal hematite particles. This effect on the particle morphology was enhanced by an increase in their molecular weight. On the other hand, the Pluronics possessing an opposite nominal formula [(PPO) x –(PEO) y –(PPO) x ] exhibited no effect on the particle shape; it only depressed phase transformation from ?-FeOOH to hematite. Not only the morphology but also the pore size of hematite particles was controlled from nonporous to mesoporous by using Pluronics. The N2 adsorption experiment and t-plot curve analysis revealed that the hematite particles changed from mesoporous to microporous by an increase in the concentration of Pluronics. On the other hand, in the presence of very low amounts of Pluronics molecules (0.1 wt.%), nonporous hematite particles were produced via strong aggregation of PN particles by their hydrogen bonding between hydroxyl and PEO or PPO groups. The dynamic light scattering measurement for the system with Pluronics clarified the existence of polynuclear (PN) particles with a hydrodynamic particle diameter (D a) of ca. 40 nm after these were aged for 6 h. The size of PN particles remained constant at ca. 40 nm during aging time of 12 h~3 days, but the scattering intensity was decreased. This decrease in the scattering intensity reveals that the number of PN particles is reduced by aggregation. The transmission electron microscope, inductively coupled plasma atomic emission spectroscopy, and total organic carbon analysis measurements employed on the systems produced for ellipsoidal particles elucidated that the formation of ellipsoidal hematite particles is attributed to the adsorption of Pluronics on the surfaces of PN and growing hematite particles. 相似文献
59.
Ishikawa N Sugita M Tanaka N Ishikawa T Koshihara SY Kaizu Y 《Inorganic chemistry》2004,43(18):5498-5500
An alternating-current (ac) magnetic susceptibility measurement for the [(Pc)(2)Tb(III)](0) complex (Pc = phthalocyaninato) has shown that ligand oxidation of the anionic [(Pc)(2)Tb(III)](-) complex gives rise to a significant upward shift of the temperature range where the magnetization response shows a phase lag behind the time-varying external magnetic field. The peaks of the out-of-phase component of the ac susceptibility of the pi-radical [(Pc)(2)Tb(III)](0) were observed at 50, 43, and 36 K with ac magnetic fields of 10(3), 10(2), and 10 Hz, respectively, which were more than 10 K higher than the corresponding values of the anionic complex with a closed-shell pi-system. The ac susceptibility measurements on the complex with octa(dodecoxy)-substituted Pc ligand, which is readily dilutable in diamagnetic media, proved that the significant rise of the temperatures occurs as an intrinsic single-molecular property of the complex possessing both J = 6 and S = (1)/(2) systems, and is not due to long-range magnetic order or interactions between adjacent unpaired pi-electrons. 相似文献
60.
Summary The asymptotic bias of the least squares estimator for the multivariate autoregressive models is derived. The formulas for
the low order univariate autoregressive models are given in terms of the simple functions of parameters. Our results are useful
to the bias correction method of the least squares estimation.
This work was supported by National Science Foundation Grant SES79-13976 at the Institute for Mathematical Studies in the
Social Sciences, Stanford University. This paper is a revision of Discussion Paper No. 504, The Center for Mathematical Studies
in Economics and Management Science, Northwestern University, October 1981. 相似文献