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1.
D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity 下载免费PDF全文
Yohei Ohkoda Akane Asaishi Tomoya Namiki Tomoaki Hashimoto Midori Yamada Koichiro Shirai Yuta Katagami Dr. Tomoaki Sugaya Prof. Makoto Tadokoro Prof. Akiharu Satake 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(33):11745-11756
The one‐step synthesis of D3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η3‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η3‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands. 相似文献
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Rikuhei Tanikaga Yoshimasa MatsumotoMaki Sakaguchi Yohei KoyamaKentaro Ono 《Tetrahedron letters》2003,44(35):6781-6783
Lipase-mediated acetylations of trans- and cis-2-substituted cyclohexanols gave the corresponding (1R)-cyclohexyl acetates and (1S)-cyclohexanols in high yields and ee, but c-4-tert-butyl-c-2-ethenyl-r-1-cyclohexanol was unreactive owing to the steric interaction between the axial OH group and the axial H atoms at the 3- and 5-positions. In the cis-isomer the OH group occupies an equatorial position to bind to the lipase, and less bulky axial alkenyl and alkynyl groups might not so much prevent acetylations than an alkyl group. 相似文献
4.
Yohei Hashimoto Masataka Moriyasu Eiko Kato Masaru Endo Naohiko Miyamoto Hiroshi Uchida 《Mikrochimica acta》1978,70(1-2):159-167
Summary A new type of detector for high-pressure liquid chromatography has been designed. This detector is equipped with a RC resonance circuit, and is similar to the capacitance detector previously reported. It is operated as a capacitance detector with nonpolar eluents; while with polar solvents, it behaves as a conductance detector. Electrolytes such as salts, acids and bases are sensitively detected. The detector was successfully used for the detection of fatty acids and alkaloids.
Zusammenfassung Ein neuartiger Detektor für die Hochdruck-Flüssigchromatographie wurde entwickelt. Dieser ist mit einem Resonanzstromkreis ausgestattet und ähnelt dem kürzlich beschriebenen Kapazitanz-Detektor. Als solcher funktioniert er mit nichtpolaren Eluenten, während er sich mit polaren Lösungsmitteln wie ein Leitfähigkeitsdetektor verhält. Salze, Säuren und Basen werden empfindlich nachgewiesen. Das Gerät wurde zum Nachweis von Fettsäuren und Alkaloiden verwendet.相似文献
5.
Yoshiyasu Ichikawa Yohei Matsukawa Mari Tamura Fumiyo Ohara Minoru Isobe Hiyoshizo Kotsuki 《化学:亚洲杂志》2006,1(5):717-723
A new method for the synthesis of urea‐linked disaccharides in aqueous media has been developed. The key feature of our approach is two strained Steyermark‐type gluco‐ and galactopyranosyl oxazolidinones. Each oxazolidinone is attached to a pyranose ring in a di‐equatorial trans‐annulation framework. Reaction of these oxazolidinones with 4‐aminohexopyranose in water proceeded smoothly to afford the urea‐tethered cellobiose and lactose analogues. The galactose‐type oxazolidinone proved to be more reactive than the glucose‐type, which is explained by the presence of an axial hydroxy group at C4 in the former. 相似文献
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Electrophoretic mobilities of red blood cells (RBCs) were measured in microgravity using a home-made capillary electrophoresis unit, which consisted of two small reservoirs of 0.6 mL and a fused-silica capillary tubing with 2 cm in length and 50 num in inner diameter. Migration of RBCs was observed by a microscope at 1000 times magnification and recorded on a videotape. The experiments were performed during stays in microgravity (about 0.01 G), which lasted 20 s and were attained by parabolic flights of an aircraft. On average, the electrophoretic mobilities of RBCs determined in microgravity were about 30% higher than those measured at 1-G condition irrespectively whether the cells were suspended in saline or serum during measurements. This difference might be explained as being mainly due to the cell floating in microgravity. Morphological changes of RBCs may contribute partly to the difference, while the variation in viscosity of the medium under microgravity could play only a minor role. 相似文献
8.
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
9.
Yoshiyuki Tanaka Makoto Arakawa Yohei Yamaguchi Chieko Hori Masahiro Ueno Takeyuki Tanaka Tatsushi Imahori Yoshinori Kondo 《化学:亚洲杂志》2006,1(4):581-585
A metal‐free acetylide was observed by using NMR spectroscopy. Metal‐free acetylides are closely related to reactive intermediates (carbanions) in solution; therefore, they have been regarded as unobservable species. However, we generated this highly reactive and unstable species through the deprotonation of phenylacetylene by using the strong nonmetallic phosphazene base tBu‐P4. In the presence of tBu‐P4, the J coupling between the ethynyl carbon and hydrogen nuclei (1JC,H) of phenylacetylene disappeared; this indicates the deprotonation of the alkyne terminal. Furthermore, a large low‐field shift (approximately 90 ppm) of the alkyne carbon resonance was observed. We concluded that we have observed a metal‐free carbanion with a formal charge on an sp‐hybridized carbon atom for the first time. 相似文献
10.
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