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Infrared spectra of CO2 sorbed in rubbery and glassy polymeric membranes were measured to examine the relationships between the spectroscopic data and the physical properties of the membranes. The two peaks observed in the spectra of CO2 were attributed to the R branch and P branch of CO2 sorbed in the membranes based on the consideration that both peaks were observed at a temperature above the glass transition temperature of the membranes. Apparent diffusion coefficients of CO2 in the membranes were measured from the desorption kinetics of CO2 detected by FTIR spectroscopy. The solubility coefficients of CO2 were also estimated from absorbance spectra of CO2 sorbed in the membranes using Lambert-Beer's rule. The permeability, solubility, and diffusion coefficients estimated by the FTIR method were found to correlate well with the coefficients obtained by conventional methods such as vacuum-pressure or sorption isotherm methods. © 1996 John Wiley & Sons, Inc.  相似文献   
123.
Synthesis and radical ring-opening polymerization of vinylcyclopropane bearing six-membered cyclic acetal moiety, 1-vinyl-4,8-dioxaspiro[2.5]octane (1), were carried out. 1 was prepared by the reaction of 1,1-dichloro-2-vinylcyclopropane and 1,3-propanediol in DMF in the presence of a base. Radical polymerization of 1 was carried out in the presence of an appropriate initiator (3 mol % vs. 1) at 60 and 120°C in degassed sealed ampoules for 20 h. A colorless transparent viscous polymer was obtained by the isolation with preparative HPLC. The structure of poly(1) was determined to consist of two 1,5-ring-opened units and a unit bearing no olefinic moiety. The difference of the activation energies for the ring-opening reaction of the cyclopropane ring calculated by the molecular orbital method could explain the selectivity in the direction of the cleavage of the cyclopropane ring. Acid hydrolysis of poly(1) afforded the corresponding polyketone in quantitative conversion. © 1996 John Wiley & Sons, Inc.  相似文献   
124.
Seventeen compounds having a variety of substituents at the 3- and 5′-positions of 2′-deoxy-5-fluorouridine (5-FUdR) and 5-fluorouridine (5-FUR) were synthesized, and their γ-radiolysis in aqueous solutions were studied. The compounds having thioureido (RNHCSNH, R  H, PhCH2, acyl) and thiocarbonylamino (XCSNH, X  PhCH2S, PhO) groups at the 3-position of 5-FUdR were efficiently cleaved to give 5-FUdR with high G values upon γ-irradiation of their aqueous solutions. The active species for these cleavage reactions were hydrated electron (e aq), H and HO. However, the compounds having a dimethylsulfoxyimino group at 3-position of 5-FUdR and 5-FUR afforded 5-FUdR and 5-FUR only under the radiolysis conditions where e aq becomes a principal active species. The compound having a 2-benzoylthiazoylthiocarbonylamino group at the 3-position of 5-FUdR showed the highest reactivity toward HO.. The mechanisms of these γ-radiolysis reactions are discussed. The examination of anticellular activities of γ-irradiated compounds having a thiocarbonylamino group at the 3-position of 5-FUdR toward murine Sarcoma 180 cells revealed that these compounds may be utilized as a candidate for a radiation-induced drug (RID).  相似文献   
125.
Helical carbazole‐based BODIPY analogues were readily synthesized via aza[7]helicenes. The structures of azahelicene‐incorporated BF2 dyes were elucidated by x‐ray diffraction analysis. DFT calculations revealed that the π‐conjugated system expanded from the helicene moiety to the BODIPY framework. The azahelicene‐fused boron complexes showed the Cotton effects and the circularly polarized luminescence (CPL) in the visible region. Furthermore, an axially chiral binaphthyl group was attached to the helically chiral dyes, which enhanced the chiroptical properties.  相似文献   
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