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21.
Taguchi Y Ohtani H Tsuge S Ishida Y Kimura K Yoshikawa T 《Journal of chromatography. A》2003,993(1-2):137-142
Highly sensitive and specific determination of trace amounts of a polymeric hindered amine light stabilizer (HALS) in polypropylene (PP) materials could be established by improving reactive thermal desorption-gas chromatography (RTD-GC) in the presence of an organic alkali, tetramethylammonium hydroxide. By using nitrogen-phosphorus detection, highly selective detection of the HALS-related components was attained. In addition, the use of a polar poly(ethylene glycol) separation column alleviated the adsorption of minor specific pyrolysis products. This modified RTD-GC method allowed the determination of the polymeric HALS (Mr 1900) in PP even for trace concentrations between 100 and 500 ppm, through observing selectively the characteristic products containing a tetramethylpiperidine moiety, which had been impossible to detect under the previous RTD-GC conditions using a non-polar separation column and conventional flame ionization detection. 相似文献
22.
Cs2CO3 was found to efficiently catalyze the reaction of β-cyclodextrin and N-tosylimidazole. Stirring β-cyclodextrin and N-tosylimidazole in 1/1.2 molar ratio in DMF in the presence of catalytic amount of Cs2CO3 at rt for 1.5 h afforded 2A-mono(O-tosyl)-β-cyclodextrin in 32% yield. The 2A,2B-, 2A,2C- and 2A,2D-ditosylates were isolated in ca. 6-7% yields, respectively, when β-cyclodextrin and N-tosylimidazole were used in 1/2.5 molar ratio. The charge of excess (10 equiv) of N-tosylimidazole ensured a one-step direct (protection-free) synthesis of the per(2-O-tosyl)-β-cyclodextrin in 5% isolated yield. N-(m-Nitrobenzenesulfonyl)imidazole even allowed a much faster access to the corresponding persulfonate in only 1 h reaction. 相似文献
23.
Yoshihiko Ohishi Tomonori Kawabata Tetsuya Shishido Ken Takaki Qinghong Zhang Ye Wang Katsuomi Takehira 《Journal of molecular catalysis. A, Chemical》2005,230(1-2):49-58
M-MCM-41 catalysts (M: V, Cr, Fe, and Ga) prepared by direct hydrothermal synthesis (DHT) have been tested for dehydrogenation of ethylbenzene with CO2. The synthesized materials were characterized by X-ray diffraction (XRD), N2 adsorption (77 K), and diffuse reflectance UV–vis spectroscopic measurements. Cr-MCM-41 showed the highest activity among M-MCM-41 catalysts tested, resulting in the production of styrene with the conversion of 65% and the selectivity above 90%. The rate of styrene formation increased with increasing Cr loading up to 1.7 wt.%. It is suggested that Cr(VI)O4 in tetrahedral coordination is formed as an active monochromate species and reduced to Cr(III)O6 in octahedral coordination as a less active polychromate species during the reaction. Deactivated catalyst was regenerated by a treatment with gaseous oxygen or CO2, during which redistribution as well as reoxidation of polymeric Cr(III)O6 octahedra to monomeric Cr(VI)O4 tetrahedra was observed. The rate of CO formation increased together with that of styrene formation, while the rate of H2 formation decreased, with increasing partial pressure of CO2. It was confirmed that reverse water-gas shift reaction took place over Cr-MCM-41 by a separate experiment. The rate of CO formation during the dehydrogenation of ethylbenzene with CO2 over Cr-MCM-41 was well accounted for by assuming parallel occurrence of two reactions, i.e., direct oxidative dehydrogenation of ethylbenzene with CO2 and simple dehydrogenation of ethylbenzene thermodynamically assisted by reverse water-gas shift reaction. 相似文献
24.
Yoshihiko Ito Yoshinori Inubushi Toru Sugaya Takeo Saegusa 《Journal of organometallic chemistry》1977,137(1):1-9
Reaction of carboxamides with Cu2O in the presence of t-butyl isocyanide gave new chelated copper(I) complexes, which probably are formed by the insertion of t-butyl isocyanide into the coppernitrogen bond of copper(I) amide isonitrile complexes, which were initially produced from the carboxamides and Cu2Ot-butyl isocyanide complex. The same chelated copper(I) complexes were prepared more readily by the reaction of the corresponding N-trimethylsilyl-carboxamides with Cu2Ot-butyl isocyanide complex. Reactions of the copper(I) complexes thus obtained with alkylating agents, such as alkyl halides, alkyl tosylates and triethyloxonium tetrafluoroborate, also were described. 相似文献
25.
Suginome M Ohmura T Miyake Y Mitani S Ito Y Murakami M 《Journal of the American Chemical Society》2003,125(37):11174-11175
Enantioenriched beta-borylallylsilanes were synthesized by palladium-catalyzed enantioface-selective addition of the silicon-boron bond to terminal allenes using a palladium catalyst possessing a chiral monodentate phosphine ligand. Use of a silylborane bearing a chiral auxiliary on the boron atom was beneficial to gain enantioface selectivities as high as 96% de. 相似文献
26.
The Hamilton dynamics of a molecule in a translationally and/or rotationally symmetric field is kept rigorously constrained in its phase space. The relevant dynamical laws should therefore be extracted from these constrained motions. An internal space that is induced by a projection of such a limited phase space onto configuration space is an intrinsically curved space even for a system of zero total angular momentum. In this paper we discuss the general effects of this curvedness on dynamics and structures of molecules in such a manner that is invariant with respect to the selection of coordinates. It is shown that the regular coordinate originally defined by Riemann is particularly useful to expose the curvature correction to the dynamics and statistical properties of molecules. These effects are significant both qualitatively and quantitatively and are studied in two aspects. One is the direct effect on dynamics: A trajectory receives a Lorentz-like force from the curved space as though it was placed in a magnetic field. The well-known problem of the trapping phenomenon at the transition state is analyzed from this point of view. By showing that the trapping force is explicitly described in terms of the curvature of the internal space, we clarify that the physical origin of the trapped motion is indeed originated from the curvature of the internal space and hence is not dependent of the selection of coordinate system. The other aspect is the effect of phase space volume arising from the curvedness: We formulate a general expression of the curvature correction of the classical density of states and extract its physical significance in the molecular geometry along with reaction rate in terms of the scalar curvature and volume loss (gain) due to the curvature. The transition state theory is reformulated from this point of view and it is applied to the structural transition of linear chain molecules in the so-called dihedral angle model. It is shown that the curvature effect becomes large roughly linearly with the size of molecule. 相似文献
27.
Imai M Sakai K Kikuchi M Nakaya K Saeki A Teramoto T 《The Journal of chemical physics》2005,122(21):214906
We have investigated the structural development during order-order transitions to the double-gyroid (DG) phase of nonionic surfactant/water systems based on two-dimensional small-angle x-ray scattering patterns from highly oriented ordered mesophases. The lamellar (L) to DG transition proceeds through two intermediate structures, a fluctuating perforated layer structure having ABAB stacking and a hexagonal perforated lamellar structure with ABCABC stacking (HPLABC). For a hexagonally packed cylinder (H) to DG transition, we also observed the HPLABC structure as the intermediate phase, thus the HPLABC is an entrance structure for the DG phase. The hexagonal perforated lamellar (HPL) structure consists of hexagonally packed holes surrounded by the planar tripods, and the transition from HPL structure to the DG phase proceeds by rotation of the dihedral angle of connected tripods. A geometrical consideration shows that large deformations of HPL planes are necessary to form the DG structure from the HPLABC structure, whereas the transition from a HPL structure with ABAB stacking (HPLAB) to the DG structure is straightforward. In spite of the topological constraints, the HPLABC structure is observed in the kinetic pathway to the DG structure. 相似文献
28.
Shintani Y Hirako K Motokawa M Iwano T Zhou X Takano Y Furuno M Minakuchi H Ueda M 《Journal of chromatography. A》2005,1073(1-2):17-23
We have developed miniaturized multi-channel high-performance liquid chromatography (HPLC) system. With this system, we can simultaneously separate multiple samples, using a single high-pressure gradient pump, a chip-based sample injection unit, a monolithic silica capillary column array, and a multi-channel UV detection unit based on fiber optics. The injection unit has a simplified structure composed of brass housing and a quartz microchip having microchannels and access ports, which enable a direct injection of sample to multi-channel by commercial multichannel micropipette. Moreover, that possesses a function of microvalve, and on-chip definition of sample injection plugs achieved with a cross channel injection method, providing each column of monolithic silica capillary array. The substances in channels were simultaneously detected with UV having multiple cells. Standard samples were analyzed for characterizing newly developed system, and sharp peaks were obtained with reproducibility data of < 0.9% (R.S.D.). Analysis of tryptic digestion of casein was also employed. These results show that the novel multi-channel HPLC system has the benefits for the high-throughput analysis in the post-genomic analysis/combinatorial chemistry. 相似文献
29.
Jun Araki Kousaku Ohkawa Yusuke Uchida Yoshihiko Murakami 《Journal of polymer science. Part A, Polymer chemistry》2012,50(3):488-494
A sliding graft copolymer (SGC) with poly(ethylene glycol) (PEG) side chains was prepared by ester formation between terminal carboxyl groups of oxidized PEG methyl ether with molecular weight of 2000 (mPEG2000‐COOH) and hydroxyl groups of a polyrotaxane consisting of PEG and cyclodextrins (CDs). Formation of the SGC structure was confirmed by 1H NMR, attenuated total reflectance Fourier‐transformed infrared, and gel permeation chromatography. The SGC was soluble in good solvents of PEG and insoluble in poor solvents of PEG. Estimation of the number of grafted mPEG chains suggested a “rope‐curtain” like structure, in which an mPEG chain is connected to each CD ring. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
30.