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61.
Eigoro Murayama Masahiro Uematsu Hiroyuki Nishio Tadashi Sato 《Tetrahedron letters》1984,25(3):313-316
Internal reaction of secondary alkyltin(IV) compounds having thionium ion gave internal trans olefins with high yield and regio- and stereoselectivity via 1,5- or 1,6-transfer of a hydride β to the trialkylstannyl group. 相似文献
62.
Large-scale separation of metallic and semiconducting single-walled carbon nanotubes 总被引:6,自引:0,他引:6
Maeda Y Kimura S Kanda M Hirashima Y Hasegawa T Wakahara T Lian Y Nakahodo T Tsuchiya T Akasaka T Lu J Zhang X Gao Z Yu Y Nagase S Kazaoui S Minami N Shimizu T Tokumoto H Saito R 《Journal of the American Chemical Society》2005,127(29):10287-10290
In the applications of single-walled carbon nanotubes (SWNTs), it is extremely important to separate semiconducting and metallic SWNTs. Although several methods have been reported for the separation, only low yields have been achieved at great expense. We show a separation method involving a dispersion-centrifugation process in a tetrahydrofuran solution of amine, which makes metallic SWNTs highly concentrated to 87% in a simple way. 相似文献
63.
Hiroyuki Hayakawa Hiromichi Tanaka Keiko Sasaki Kazuhiro Haraguchi Takafumi Saitoh Fumi Takai Tadashi Miyasaka 《Journal of heterocyclic chemistry》1989,26(1):189-192
Several 8-substituted cordycepins were prepared via LDA lithiation of 2′,5′-bis-O-(t-butyldimethylsilyl)-cordycepin and successive reactions of its C-8 lithiated species with various types of electrophiles. Wittig reaction of the 8-formyl derivative was also examined. 相似文献
64.
Summary The “chemical” relaxation of stress either in Amilan (6-Nylon) or polyvinyl alcohol caused by penetration of water vapor was
studied at 40% R. H. and temperatures 15, 30, and 50° C. A theory was presented of the chemical relaxation in a polymer which
comprises penetrant-sensitive bonds as the crosslinkages between the molecular chains. This theory assumes the diffusion coefficient
of penetrant in the polymer to he independent of concentration and any other factors. It was found that the system Amilan-water
behaves in exact conformity with the theory over the ranges of elongation and temperature studied. The diffusion coefficient,D, of water in Amilan could thus be evaluated from the chemical relaxation data, using the theory presented, as functions of
elongation and temperature. An ordinary sorption experiment was carried out for this system at 40% R. H. and 16.8° C and demonstrated
that the diffusion of water in Amilan was Fickian with a constant diffusion coefficient. Both diffusion coefficients from
the chemical relaxation data and the sorption. data were found to agree quite well when the former was extrapolated to zero-strain.
The chemical relaxation behavior in the system polyvinyl alcohol-water was markedly different from that expected from the
theory, suggesting primarily that the diffusion coefficient of water in this polymer was not constant. A parallel evidence
for this fact was obtained from sorption measurements on this system, which demonstrated the diffusion in this system to be
dependent both on concentration and time.
From these results it may be concluded that the chemical relaxation technique, when combined properly with an adequate theory,
can be used not only to evaluate the diffusion coefficient of penetrant in a given polymer solid but also to investigate,
at least qualitatively, the type of sorption behavior characteristic of the system under given experimental conditions.
Zusammenfassung Die chemische Spannungsrelaxation in Amilan (6-Nylon) und Polyvinylalkohol, verursacht durch Eindringen von Wasserdampf, wurde bei 40% r. F. und Temperaturen von 15, 30 und 50° C untersucht. Es wird eine Theorie der chemischen Relaxation von Polymeren vorgelegt, die als empfindliche Bindungen auf das eindringende Niedermolekulare die Vernetzungen zwischen den molekularen Ketten betrachtet. Diese Theorie setzt voraus, da? der Diffusionskoeffizient im Polymeren für die eindringende Substanz unabh?ngig von Konzentration und anderen Faktoren ist. Das System Amilan-Wasser benimmt sich vollkommen entsprechend dieser Theorie in den studierten Verstreckungs- und Temperaturbereiche. Der Diffusionskoeffizient von Wasser in Amilan konnte daher aus der chemischen Relaxation als Funktion von Dehnung und Temperatur ausgewertet werden. Ein normales Quellungsexperiment wurde für das System bei 40% r. F. und 16,8° C ausgeführt und zeigte, da? die Diffusion von Wasser in Amilan dem Fickschen Gesetz mit konstantem Diffusionskoeffizienten folgt. Beide Diffusionskoeffizienten, der aus chemischer Relaxation und der aus Quellungsdaten gewonnene, stimmten sehr gut überein, falls der erstere auf die Dehnung 0 extrapoliert wurde. Die chemische Relaxation des Systems Polyvinylalkohol-Wasser war merklich anders als nach der Theorie erwartet und lie? in erster Linie vermuten, da? der Diffusionskoeffizient von Wasser in diesem Polymeren nicht konstant ist. Eine entsprechende Andeutung wurde aus Quellungsmessungen an diesem System erhalten. Die Diffusion h?ngt von Konzentration und Zeit ab. Aus diesen Resultaten kann gefolgert werden, da? die Technik der Untersuchungen der chemischen Relaxation unter Verwendung einer geeigneten Theorie nicht nur dazu angewendet werden kann, Diffusionskoeffizienten von kleinen Molekülen in einem gegebenen festen Polymeren zu messen, sondern zumindest auch qualitativ den Typ des Quellungsverhaltens festzustellen, der das System unter den gegebenen experimentellen Bedingungen charakterisiert.相似文献
65.
2,3-Dideoxy-3-fluoro-α-d-ribose 1-phosphate 2 was stereoselectively synthesized and converted to 2′,3′-dideoxy-3-fluoro-β-d-guanosine 1 by enzymatic reaction using purine nucleoside phosphorylase. This chemo-enzymatic strategy was first applied to the synthesis of 1. 相似文献
66.
Toshio Takido Sachiko Tamura Kenji Sato Haruo Kamijo Toshikatsu Nakazawa Manabu Seno Tadashi Hata 《Journal of heterocyclic chemistry》1998,35(2):437-443
The synthesis of hexahydrooxoepithiopyridinedicarboxyimide (5: X2 = N-Ph) by the reaction of thioamides 1 with N-substituted maleimide ( 2a ) was examined. The reaction of primary thioamides, such as thiobenzamide and p-toluthioamide with N-phenylmaleimide gives compounds 5 together with corresponding 4-hydroxy-1,3-thiazoles 4 . However, a similar reaction of secondary thioamides, such as N-methylthioacetamide, thiobenzanilide, with N-phenylmaleimide did not provide compounds 5 without addition of acid. The reaction pathway and the configuration of 5 were also investigated. 相似文献
67.
In the present paper, a study was undertaken of molecular transport in ploy(dimethylsiloxane) microchannels that were fabricated by ultraviolet (UV)-photolithography and synchrotron radiation (SR)-lithography characterized and compared for microchip capillary electrophoresis by evaluating in-channel molecular dispersion. A fluorescent tag, sulforhodamine B was used as the probing molecule. It was found that microchannels made by SR-lithography fabrication were superior to those made by UV-photolithography fabrication in terms of molecular transport performance. A deep insight into surface conditions characterized by scanning electron microscopy suggested it was related to the difference in surface roughness. Chromatographic retention in electropherograms further supported such a conclusion, which depended on the phase ratio of the channel surface. The results revealed for PDMS microchannels in this work were in good agreement with the phenomenon found for glass microchannels in the literature. 相似文献
68.
Collision energy dependence of partial ionization cross sections (CEDPICS) of p-benzoquinone with He(*)(2 (3)S) metastable atoms indicates that interaction potentials between p-benzoquinone and He(*)(2 (3)S) are highly anisotropic in the studied collision energy range (100-250 meV). Attractive interactions were found around the C==O groups for in-plane and out-of-plane directions, while repulsive interactions were found around CH bonds and the benzenoid ring. Assignment of the first four ionic states of p-benzoquinone and an analogous methyl-substituted compound was examined with CEDPICS and anisotropic distributions of the corresponding two nonbonding oxygen orbitals (n(O) (+),n(O) (-)) and two pi(CC) orbitals (pi(CC) (+),pi(CC) (-)). An extra band that shows negative CEDPICS was observed at ca. 7.2 eV in Penning ionization electron spectrum. 相似文献
69.
Tadashi Arii Kiyoshi Terayama Nobuyuki Fujii 《Journal of Thermal Analysis and Calorimetry》1996,46(6):1821-1836
Controlled-rate thermal analysis (CRTA) and differential scanning calorimetry (DSC) were used to investigate the adsorbed water layers and the surface properties of different commercial activated carbons. A simple method is proposed to obtain information on the properties of the adsorbed water film and the surface heterogeneity of the materials studied. This method utilizes TG mass loss and the first derivative of the DTG mass loss curves with respect to temperature and time, obtained during programmed liquid thermodesorption. The obtained TG mass loss curves, which reflect the energetic heterogeneity, consisted of steps and inflections which were associated with the mechanism of wetting of the solid surfaces. The heights of these steps and inflections depend on the adsorption capacity, the adsorption potential and the nature and number of the active centers of the carbon samples studied. The values of the total porosity and the surface phase capacity obtained by this method are in good agreement with those estimated on the basis of independent methods. The behaviour of water/carbon samples was studied by means of DSC at subambient and elevated temperatures. The experimental results provided novel data on the structural heterogeneity, the thermal stability of the water/carbon interface and its phase and structural transitions.Support from the Research Council of Kent State University (Ohio, USA) is acknowledged. The author is pleased to thank Drs M. Jaroniec, R. K. Gilpin, J. Choma and R. Dobrowolski for fruitful discussions and the active carbon samples. 相似文献
70.
Akira Nishinaga Toshio Itahara Tadashi Shimizu Haruo Tomita Kanji Nishizawa Teruo Matsuura 《Photochemistry and photobiology》1978,28(4-5):687-692
Abstract— The mechanisms by which 4-substituted 2,6-di- t -butylphenols are oxygenated by base- and Co(II) Schiff base complex-catalysis into o - or p -peroxyquinols and their Co(III) complexes, respectively, have been investigated. For the base-catalyzed oxygenation, a one-step ionic mechanism involving no radical species is suggested to be the most probable one. For the formation of the peroxycobalt(III) complexes, the following stoichiometry is concluded: ArOH + Co(II) + 5/4 O2 → peroxycobalt(III) complex + 1/2 H2 O. A mechanism involving an electron transfer between the phenols and the Co(II)-O2 complex followed by further electron transfer between the formed phenoxy radicals and the Co(II) complex to give the corresponding phenolate anions is proposed. 相似文献