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21.
Yoh Kodera Ayako Ajima Katsunobu Takahashi Ayako Matsushima Yuji Saito Yuji Inada 《Photochemistry and photobiology》1988,47(2):221-223
Abstract— Hematoporphyrin, having two carboxylic groups, was coupled with α-(3-aminopropyl)-ω-methoxypoly(oxyethylene), PEG-NH2 , through acid-amide bond formed with carbodtimide. PEG-modified hematoporphyrin was readily soluble not only in neutral aqueous solution but also in organic solvents. Its absorption spectrum showed a sharp band at 376 nm in neutral aqueous solution and at 403 nm in benzene. Modified hematoporphyrin acted as a photosensitizer; imidazole and indole were photooxidized in organic solvents such as benzene or chloroform, and uric acid was also photooxidized in neutral aqueous solution. 相似文献
22.
Yoshitaka Ogiwara Hitoshi Kubota Yuji Kimura 《Journal of polymer science. Part A, Polymer chemistry》1978,16(11):2865-2873
The influence of ferric acetylacetonate [Fe(acac)3] on the photodegradation of model compounds of polyethylene (PE) was examined. By studying electron-spin-resonance (ESR) spectra of photoirradiated compounds such as 1-octene and 1,7-octadiene, which contain carbon double bonds, Fe(acac)3 was found to accelerate the formation of allyl radical by contact with them. On the other hand, Fe(acac)3 suppressed the radical formation based on Norrish type I reaction in a carbonyl group of compounds such as 2-octanone and 3-octanone. Based on the study of ultraviolet (UV) spectra as well as ESR spectra on photoirradiated samples, the influence of Fe(acac)3 on the photodecomposition of model compounds of PE was discussed. Finally, the discussion turned to the mechanism of photodecomposition of PE in the presence of ferric salt. 相似文献
23.
Photooxygenations of 4-2H-anisole () and o-xylene () by 3-methylpyridazine 2-oxide () or pyridine 1-oxide () were studied in a variety of solvents at varying irradiation temperatures. Remarkable solvent effect on NIH-shift coupled with their hydroxylation processes was observed. 相似文献
24.
Stephanie L. Brock Tomoko Shimojo Steven L. Suib Yuji Hayashi Hiroshige Matsumoto 《Research on Chemical Intermediates》2002,28(1):13-24
Methane conversions of 11.9%, yields of hydrogen as high as 23.3% and energy yields of 1.0 mol H2/kWh have been achieved from CO2 reforming of CH4 in non-thermal, atmospheric pressure plasma reactors with Pt coated electrodes. Two reactors have been studied. A novel fan type reactor consisting of a movable rotor and immobile stator produced the highest yields in contrast to a tube type (silent discharge) reactor with a glass dielectric barrier. Conversions, yields of hydrogen and energy yields (expressed as mol H2/kWh) were studied for CO2/CH4 concentrations of 1.1% and 5.0% in He as a function of flow rate and input voltage. Hydrogen yields are observed to increase as the input voltage is increased from 411 V to 911 V and the flow rate is decreased from 100 cc/min to 30 cc/min. Energy yields vary only slightly with input voltage and flow rate. Hydrogen yields show little dependence on CO2/CH4 concentrations, but energy yields are approximately five times greater for the 5.0% mixture than the 1.1% mixture. Selectivities to H2, CO, coke, and low molecular weight hydrocarbons were also evaluated and compared to data obtained without CO2 in the feed. Hydrogen selectivities of nearly 100% were obtained, with small amounts of ethane and propane as the only observed side products and the selectivites were approximately the same whether CO2 was present or absent in the mixture. However, the reaction proceeds much more cleanly when CO2 is present, producing CO. The syngas product has an H2 : CO ratio of 1.5 with the fan type reactor and 0.67 with the tubular reactor. In the absence of CO2, coke is the main carbonaceous product. Under all conditions studied the fan type reactor demonstrated higher methane conversions (up to 11.9%) and selectivities to hydrogen. 相似文献
25.
Takashima H Mimura N Ohkubo T Yoshida T Tamaoki H Kobayashi Y 《Journal of the American Chemical Society》2004,126(14):4504-4505
Distributed computing has been implemented to the solution structure determination of endothelin-1 to evaluate efficiency of the method for NMR constraint-based structure calculations. A key target of the investigation was determination of the C-terminal folding of the peptide, which had been dispersed in previous studies of NMR, despite its pharmacological significances. With use of tens of thousands of random initial structures to explore the conformational space comprehensively, we determined high-resolution structures with good convergences of C-terminal as well as previously defined N-terminal structures. The previous studies had missed the C-terminal convergence because of initial structure dependencies trapped in localized folding of the N-terminal region, which are strongly constricted by two disulfide bonds. 相似文献
26.
27.
Masahiro Kurokawa Hidemasa Yamaguchi Yuji Minoura 《Journal of polymer science. Part A, Polymer chemistry》1979,17(2):485-492
l-Menthyl vinyl ether (l-MVE) was homopolymerized and copolymerized with the monomers indene (IN) and acenaphthylene (ANp) by BF3OEt2 as a catalyst. The chiral menthyl substituent was cloven from the homopolymers and copolymers using dry-hydrogen bromide gas. After the removal of optically active menthyl group, poly(vinyl alcohol) (PVA) from l-MVE homopolymer was optically inactive, and copolymers (VA-IN, VA-ANp) from l-MVE-IN and l-MVE-ANp copolymers were still optically active. Hence, in the case of l-MVE homopolymer, it was concluded that asymmetric induction in the polymer main chain can only produce pseudoasymmetry. In the case of l-MVE-IN and l-MVE-ANp copolymers, it was found that asymmetric induction proceeded in the copolymer main chain and was caused by the influence of chiral menthyl group. 相似文献
28.
Masahiro Kurokawa Yuji Minoura 《Journal of polymer science. Part A, Polymer chemistry》1979,17(10):3297-3305
The copolymerizations of l-menthyl vinyl ether (l-MVE) with the monomers vinylene carbonate (VCA) and indene (IN) were carried out in benzene with azobisisobutyronitrile (AIBN) as an initiator to obtain optically active copolymers. The optically active l-menthyl residue from the copolymer main chain was removed using dry hydrogen bromide gas. After the ether cleavage reaction, the copolymers prepared (VA–VCA and VA–IN) were still optically active, and hence it was found that asymmetric induction had taken place in the copolymer main chain. The optical rotatory dispersion (ORD) and circular dichroism (CD) data of the original and ether-cloven copolymers were also determined. 相似文献
29.
Ramesh P Okazaki T Taniguchi R Kimura J Sugai T Sato K Ozeki Y Shinohara H 《The journal of physical chemistry. B》2005,109(3):1141-1147
Double-wall carbon nanotubes (DWNTs) have been selectively synthesized over Fe/Co loaded mesoporous silica by catalytic chemical vapor deposition of alcohol. Several silica materials with desired pore diameter and morphology have been investigated for the DWNT growth. The diameter distribution and selectivity of the DWNT are found to depend on the reaction temperature, pore size, and thermal stability of the support material. A high-yield synthesis of DWNTs has been achieved at 900 degrees C over high-temperature stable mesoporous silica. The outer diameter of DWNTs is found to be in the range of 1.5-5.4 nm with a "d" spacing of 0.38 +/- 0.02 nm between inner and outer layers, which is much larger than those of multiwall carbon nanotubes. 相似文献
30.
Kubo Y Tokita S Kojima Y Osano YT Matsuzaki T 《The Journal of organic chemistry》1996,61(11):3758-3765
A new family of indoaniline-derived calix[4]arenes has been synthesized for the purpose of developing a new chromogenic receptor. A condensing reaction of calix[4]arene (1) with 4-(diethylamino)-2-methylaniline hydrochloride (2) in the presence of an oxidizing agent under alkaline conditions affords mono- (3), 1,2-bis- (4), 1,3-bis- (5), and tetrakisindoaniline-derived (6) calix[4]arenes after careful column chromatography. Compound 3 is crystallized from a CHCl(3)-MeOH solution, and the crystal structure was determined by X-ray analysis. The crystal is monoclinic, space group P2(1)/n, Z = 4, a = 19.507(6) ?, b = 18.591(6) ?, c = 8.524(2) ?, beta = 94.69(2) degrees. The final R value for 2406 reflections of F(o) > 3sigma(F(o)) is 0.085. A unique intramolecular hydrogen-bonding network involving the carbonyl oxygen of indoaniline for 3 implied that the quinone carbonyl group as an acceptor of the chromophore can easily be subjected to an electrostatic interaction in the lower rim. Indeed, 1,3-bis(indoaniline)-derived 2,4-bis((ethoxycarbonyl)methoxy)calix[4]arene 7, prepared by the reaction of 5 with ethyl bromoacetate in the presence of NaH, is capable of undergoing an efficient ion-dipole interaction between the binding cation and the two quinone carbonyl groups of the chromophores, so that a selective Ca(2+)-induced pronounced color change (wavelength change > 100 nm) occurs with an association constant on the order of 10(6) in 99% EtOH, making 7 of potential use as an optical sensor for Ca(2+) detection. The IR and NMR studies have indicated that Ca(2+) is encapsulated in the cavity made by the distally located OCH(2)CO(2) groups on the lower rim of the cone-shaped calix[4]arene segment. Interestingly, however, the shape of the cavity in which Ca(2+) has been encapsulated does not have a C(2) axis of symmetry, as inferred from the (1)H-(1)H COSY experiment. On the other hand, 1,2-bis(indoaniline)-derived analogue 8 shows no response with metal ions, which can be interpreted to mean the absence of a cavity for encapsulation on the lower rim. 相似文献