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61.
Hitoshi Kubota Yoshitaka Ogiwara Kei Matsuzaki 《Journal of polymer science. Part A, Polymer chemistry》1974,12(12):2809-2819
The decay behavior of cellulose radicals produced by photo-irradiation at room temperature and the characteristics of photo-irradiated cellulose samples to initiate graft copolymerization of methyl methacrylate (MMA) were investigated. ESR spectra of such untreated, swollen, oximated, and ferric ion-sensitized samples irradiated at room temperature were constructed mainly of a single absorption line with a line width of 20 to 22 gauss and a g value of 2.003, and it is surely conceivable that the radicals showing a singlet spectrum should agree with those of alkoxy end produced at either the C1 or C4 position of the glucose unit by the scission of glucosidic bonds. The decay of radicals was accelerated by contact of various solvents with the samples, the activity decreasing in the order, water ≈ methanol ? acetone > dioxane. On the other hand, the decay of radicals by vinyl monomers became smaller in the order, methacrylic acid > MMA ≈ styrene. Graft copolymerization of MMA by a photo-irradiated sample was effectively initiated with the use of a certain amount of water or methanol, but not with acetone and dioxane. As no initiation can occur with the unirradiated sample, it is concluded that the initiation of graft copolymerization on the photo-irradiated sample is attributable to cellulose radicals showing a singlet spectrum which are formed in photo-irradiation at room temperature. 相似文献
62.
Mitsuru Ueda Toshitaka Koyama Motokazu Mano Masahiko Yazawa 《Journal of polymer science. Part A, Polymer chemistry》1989,27(3):751-762
Ethyl α-hydroxymethylacrylate (EHMA) was synthesized and homopolymerized in bulk and in solution. The poly(EHMA) is readily soluble in alcohol, acetone, tetrahydrofuran, and methylene chloride at room temperature. Intramolecular lactone formation occurred when poly(EHMA) was heated to 180–230°C. The kinetics of EHMA homopolymerization was investigated in ethyl acetate, using α,α′-azobisisobutylonitrile as an initiator. The rate of polymerization Rp was expressed by Rp = k[AIBN]0.50[EHMA]1.4 and the overall activation energy was calculated as 71.9 kJ/mol. Kinetic constants for EHMA polymerization were obtained as follows: kp/k = 0.17L0.9mol?0.9s?0.5; 2fkd = 1.5 × 10?5 s?1. The relative reactivity ratios of EHMA(M2) copolymerization with styrene (r1 = 0.472, r2 = 0.564) in ethyl acetate were obtained. Applying the Q-e scheme led to Q = 0.84 and e = 0.35 for EHMA. 相似文献
63.
The coordination around the thorium(IV) ion in aqueous perchlorate, chloride and nitrate solutions has been determined from large angle X-ray scattering measurements. In perchlorate solutions, where inner-sphere complexes are not formed, the first coordination sphere contains 8.0±0.5 water molecules with Th-H2O bond lengths of 2.485 Å. In chloride solutions inner-sphere complexes are formed, which lead to an increase in the coordination number. In nitrate solutions the nitrate ions are bonded as bidentate ligands to the thorium ion. The bond lengths are similar to those found in crystalline hydrates of thorium nitrate. The coordination numbers found for thorium(IV) in solution are compared with previously reported values for lower charged ions of similar size.On leave from Department of Inorganic Chemistry Royal Institute of Technology S-10044 Stockholm Sweden 相似文献
64.
Hisanobu Wakita Georg Johansson Magnus Sandström Peter L. Goggin Hitoshi Ohtaki 《Journal of solution chemistry》1991,20(7):643-668
Structures of the complexes formed in aqueous solutions between zinc(II) and iodide ions have been determined from large-angle X-ray scattering, Raman and far-IR measurements. The coordination in the hydrated Zn2+ hexaaqua ion and the first iodide complex, [ZnI]+, is octahedral, but is changed into tetrahedral in the higher complexes, [ZnI2(H2O)2], [ZnI3(H2O)]– and [ZnI4]2–. The Zn-I bond length is 2.635(4)Å in the [ZnI4]2– ion and slightly shorter, 2.592(6)Å, in the two lower tetrahedral complexes. In the octahedral [ZnI(H2O)5]+ complex the Zn-I bond length is 2.90(1)Å. The Zn-O bonding distances in the complexes are approximately the same as that in the hydrated Zn2+ ion, 2.10(1)Å. 相似文献
65.
66.
67.
Four new cycloartane glycosides from Aquilegia vulgaris 总被引:2,自引:0,他引:2
Four new cycloartane glycosides, named aquilegiosides G-J, were isolated from the dried aerial parts of Aquilegia vulgaris. Their structures were determined by spectroscopic analysis and chemical evidence. 相似文献
68.
Shokyoku Kanaoka Nobuyuki Ikeda Akira Tanaka Hitoshi Yamaoka Toshinobu Higashimura 《Journal of polymer science. Part A, Polymer chemistry》2002,40(14):2449-2457
Random copolymers with high molecular weights of indene and p‐methylstyrene (pMeSt) were synthesized by cationic polymerization with trichloroacetic acid/tin tetrachloride in CH2Cl2 at low temperatures. When indene and pMeSt (1:1 v/v), for example, were polymerized at ?40 °C, both monomers were consumed at very similar rates to give a copolymer with high molecular weight [number‐average molecular weight (Mn): 8–9 × 104]. This is indeed quite unexpected behavior for the combination of these two monomers because pMeSt polymerized over 1000 times faster than indene in the homopolymerization under the reaction conditions previously described. The product copolymer of indene and pMeSt had a random monomer sequence in it that was confirmed by NMR analyses and thermal‐property measurements. In sharp contrast with pMeSt, styrene and p‐chlorostyrene, which have no electron‐donating groups on the phenyl ring, led to low molecular weight polymers (Mn < 10,000) in the copolymerization with indene (1:1 v/v). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2449–2457, 2002 相似文献
69.
Extraction equilibria for the 4-(2-Pyridylazo)-Resorcinol-Nickel(II)-Quaternary-Ammonium salt system
The extraction equilibria of nickel(II)-PAR complexes with tetradecyldimethylbenzylammonium chloride(Q+Cl?) are investigated. Two kinds of nickel complex are extracted by chloroform: Ni(HR)2,nQ+Cl?(0)(?500 = 3.73·104l mol?1cm?1) at about pH 5 and 2Q+ NiR2-2(o)(?500 = 8.08·104 l mol?1 cm?1) at above pH 8.5. The extraction constant for 2Q+ NiR2-2(o) was evaluated as [2Q+ NiR2-2]0/[NiR2-2] [Q+]2 = 1011.16 at μ = 0.1 (Na2SO4. Synergic extraction studies of the Ni(HR)2 species under slightly acidic conditions show that the species is Ni(HR)2(H2O)2in auqeous solution and is extracted into chloroform as the adduct Ni(HR)2(TBP)2 (?535 = 3.57·104 l mol?1 cm?1. Based on the extraction behavior of these complexes, the structures of the Ni2+—PAR complexes are discussed. 相似文献
70.
ESTIMATION OF AN INDEX OF HYDROPHOBICITY OF DNA INTERIOR USING 5-METHOXYPSORALEN AS A FLUORESCENT PROBE 总被引:1,自引:0,他引:1
Masako Sasaki Isao Nakasato Hiroyuki Sugiura Hitoshi Fujita Toshibumi Sakata 《Photochemistry and photobiology》1987,46(4):551-555
The index of hydrophobicity of DNA interior was estimated by measuring fluorescence spectra of psoralen derivatives associated with DNA. The environment around 5-MOP associated with DNA was as hydrophobic (Dk = 34) as methanol, suggesting that the molecules reside at the space between the base-pairs in B-form DNA. This is also true for 8-MOP. Thus, planar and aromatic molecules of 5- and 8-MOP are more stable in the interior of DNA than in aqueous medium due to hydrophobic affinity. 相似文献