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31.
Ayumi Yoshida Hitoshi Yamauchi Hideki Sakai Norimichi Kawashima Masahiko Abe 《Colloids and surfaces. B, Biointerfaces》1997,8(6):191-342
Molecular interactions between lipid bilayers (liposomes) and chondroitin sulfate C (CS), a water soluble polymer, have been investigated in terms of zeta-potential, particle size, microscopic-viscosity, microscopic-polarity of liposomes and permeability of calcein. Microscopic morphology is dramatically changed by the addition of CS to the positively charged liposomes (Pos.L), while it is not changed by the addition to uncharged liposomes (Unc.L) or negatively charged liposomes (Neg.L). The absolute value of the particle size of Pos.L increases with the addition of CS, while the zeta- potential of Pos.L decreases. Permeability of Pos.L decreases with an increase in the concentration of CS. Phase transition temperature of Pos.L is changed after the addition of CS. These values, however, are not changed for the other liposomes by the addition of CS. The results of gel filtration chromatography show that CS is absorbed on the Pos.L surface. Microscopic viscosity is also increased by the addition of CS to Pos.L due to the adsorption of CS. 相似文献
32.
The mechanism for the activation of the sigma bonds, the O-H of H2O, C-H of CH4, and the H-H of H2, and the pi bonds, the C[triple bond]C of C2H2, C=C of C2H4, and the C=O of HCHO, at the Pd=X (X = Sn, Si, C) bonds of the model complexes (H2PC2H4PH2)Pd=XH2 5 has been theoretically investigated using a density functional method (B3LYP). The reaction is significantly affected by the electronic nature of the Pd=X bond, and the mechanism is changed depending on the atom X. The activation of the O-H bond with the lone pair electron is heterolytic at the Pd=X (X = Sn, Si) bonds, while it is homolytic at the Pd=C bond. The C-H and H-H bonds without the lone pair electron are also heterolytically activated at the Pd=X bonds independent of the atom X, where the hydrogen is extracted as a proton by the Pd atom in the case of X = Sn, Si and by the C atom in the case of X=C because the nucleophile is switched between the Pd and X atoms depending on the atom X. In contrast, the pi bond activation of C[triple bond]C and C=C at the Pd=Sn bond proceeds homolytically, and is accompanied by the rotation of the (H2PC2H4PH2)Pd group around the Pd-Sn axis to successfully complete the reaction by both the electron donation from the pi orbital to Sn p orbital and the back-donation from the Pd dpi orbital to the pi orbital. On the other hand, the activation of the C=O pi bond with the lone pair electron at the Pd=Sn bond has two reaction pathways: one is homolytic with the rotation of the (H2PC2H4PH2)Pd group and the other is heterolytic without the rotation. The role of the ligands controlling the activation mechanism, which is heterolytic or homolytic, is discussed. 相似文献
33.
[reaction: see text] Ab initio calculations using 6-311G**, cc-pVDZ, aug-cc-pVDZ, and a (valence) double-zeta pseudopotential (DZP) basis set, with (QCISD, CCSD(T)) and without (UHF) the inclusion of electron correlation, and density functional methods (BHandHLYP, B3LYP) predict that alpha,beta-unsaturated acyl radicals and alpha-ketenyl radicals exist as isomers. At the CCSD(T)/cc-pVDZ//BHandHLY/cc-pVDZ level of theory, energy barriers of 15.1 and 17.7-21.7 kJ mol(-)(1) are calculated for the isomerization of s-trans-propenoyl and s-trans-crotonoyl radical to ketenylmethyl and 1-ketenylethyl radical, respectively. Similar results are obtained for the reactions of s-trans isomers involving silyl, germyl, and stannyl groups with energy barriers (DeltaE++) of 12.2-12.4, 13.1-13.9, and 12.9-18.2 kJ mol(-)(1) at the CCSD(T)/DZP//BHandHLYP/DZP calculation, respectively. These results suggest that alpha,beta-unsaturated acyl radicals and alpha-ketenyl radicals are not canonical forms but are isomeric species that can rapidly interconvert. 相似文献
34.
(R)-Tetrahydrozerumbone 2, which has a powerful balmy fragrance, contains a stereogenic carbon at the C2 position and can be easily prepared from zerumbone 1, one of the most important materials displaying an NMRDOS character. The reduction of 2 gave two diastereomers of tetrahydrozerumbol 3, and the optically active (>99%ee) alcohols were obtained by a lipase-catalyzed stereoselective transesterification of each racemic alcohol. A barrier to this development is a long reaction time (about four weeks) and the need to separate the diastereoisomers. The desired (2R)-form of 3 was efficiently obtained by a lipase-catalyzed transesterification under optimized conditions using a diastereomeric mixture of racemic 3 as the starting material without separation of the diastereomers. Using this method, the reaction of other zerumbone derivatives is greatly improved. 相似文献
35.
Jun-Ichi Asakura Masakuni Yoshihara Takaaki Shindo Yoshio Matsubara Toshihisa Maeshima 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(3):371-377
The radical copolymerization of vinylidene chloride (Vc, M1) with 3(2-methyl)-6-methylpyridazinone (I, M2) was carried out in benzene, ethanol, phenol, and acetic acid at 60 and 80°C. The monomer reactivity ratios were found to vary with the reaction conditions. The linear correlationships were obtained by plotting the values of log r1 against those of V C[dbnd]O and V C[dbnd]C of monomers determined in the solvents. 相似文献
36.
Ayumi Suzuki Dr. Yuichiro Mutoh Dr. Noriko Tsuchida Chi-Wai Fung Dr. Shoko Kikkawa Prof. Isao Azumaya Prof. Shinichi Saito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(17):3795-3802
Although the chemistry of transition-metal complexes with carbonyl (CO) and thiocarbonyl (CS) ligands has been well developed, their heavier analogues, namely selenocarbonyl (CSe) and tellurocarbonyl (CTe) complexes remain scarce. The limited availability of such CSe and CTe complexes has so far hampered our understanding of the differences between such chalcogenocarbonyl (CE: E=O, S, Se, Te) ligands. Herein, we report the synthesis and properties of a series of cationic half-sandwich ruthenium CE complexes of the type [CpRu(CE)(H2IMes)(CNCH2Ts)][BArF4] (Cp=η5-C5H5−; H2IMes=1,3-dimesitylimidazolin-2-ylidene; ArF=3,5-(CF3)2C6H3). A combination of X-ray diffraction analyses, NMR spectroscopic analyses, and DFT calculations revealed an increasing π-accepting ability of the CE ligands in the order O<S<Se<Te. A variable-temperature NMR analysis of the thus obtained chiral-at-metal CE complexes indicated high stereochemical stability. 相似文献
37.
Jun-Ichi Asakura Masakuni Yoshihara Yoshio Matsubara Toshihisa Maeshima 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(8):1473-1478
Radical copolymerization of styrene (St, M1) with acrylonitrile (AN, M2) has been carried out using azobisisobutylonitrile as an initiator in benzene, dimethylsulfoxide, acetonitrile, and ethanol at 60 and 80°C. Good linear correlationships were obtained by plotting the values of log r1, log r2, Q2, and e2 against those of vC[dbnd]N and vC[dbnd]C determined in the solvents: the increase in the interaction between AN and the solvent was found to decrease the values of log r1 and e2 but to increase those of log r2 and Q2. The results are discussed in terms of the solvation both in the ground state and in the transition state. 相似文献
38.
Hirohito Ikeda Yukiko Sano Tomonori Matsubara Mitsunobu Kawahara Miho Yukawa Masao Fujisawa Eiji Yukawa Hatsumi Aki 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1135-1138
Propericiazine (PCZ) is an antipsychotic agent used for the treatment and the prevention of relapse of schizophrenia. We found that when an oral solution containing PCZ was mixed with a green tea drink, the residual content of PCZ was reduced by forming an insoluble complex between PCZ and tea polyphenol. In this study, the mechanism underlying the incompatibility of PCZ with green tea polyphenol (GTP) in the solution was clarified by isothermal titration microcalorimetry (ITC). Both solutions of 27.4 mM PCZ and 2.2 mM (?)-epigallocatechin gallate (EGCg), which is a main ingredient of GTP, were mixed and then PCZ in the filtrate was reduced to approximately 60 %. According to measurement at 298 K by ITC, PCZ formed an insoluble complex with EGCg at an associate constant (K) of 4.75 × 102 M?1 exothermically, ΔH = ?40.0 kJ mol?1. When (?)-epicatechin gallate (ECg) was used as the GTP, PCZ interacted with ECg with K and ΔH values of 3.74 × 102 M?1 and ?22.1 kJ mol?1, respectively. On the other hand, little heat of the reaction between PCZ and (?)-epigallocatechin or (?)-epicatechin was observed. The results indicated that the main reason for this incompatibility was the formation of an insoluble complex by PCZ and a gallate-type GTP such as EGCg and ECg in the aqueous solution. 相似文献
39.
Masaru Asari Kumiko Oka Tomohiro Omura Chikatoshi Maseda Yoshikazu Tasaki Hiroshi Shiono Kazuo Matsubara Mitsuyoshi Matsuda Keiko Shimizu 《Electrophoresis》2013,34(3):448-455
Amplification/hybridization‐based genetic analyses using primers containing locked nucleic acids (LNAs) present many benefits. Here, we developed a novel design for universal fluorescent PCR using LNAs. Universal fluorescent PCR generates intermediate nonlabeled fragments and final fluorescent fragments in a two‐step amplification process that uses locus‐specific primers with universal tails and universal fluorescent primers. In this study, a few standard nucleotides were replaced with LNAs only in the fluorescent universal primers. The sequence of the fluorescent universal primer significantly affected the amplification efficiency. For primers with three LNAs, the fluorescent primers with stable M13(‐47) sequences provided the most efficient signal (approximately tenfold higher than the primers with M13(‐21) sequences at lower Tm values). Moreover, AT‐rich LNA substitutions in the fluorescent primers produced much lower amplification efficiencies than GC‐rich substitutions. GC‐rich LNAs produced greater differences in Tm values among primers, and resulted in the preferential production of fluorescently labeled amplicons. The specificity and sensitivity of LNA‐containing fluorescent primers were assessed by genotyping eight STRs in Japanese individuals, and full STR profiles could be generated using as little as 0.25 ng of genomic DNA. The method permitted clear discrimination of alleles and represents sensitive STR genotyping at a reduced cost. 相似文献
40.
Huihui Li Yosuke Imai Takanori Takiue Hiroki Matsubara Makoto Aratono 《Colloid and polymer science》2014,292(5):1209-1215
The composition of the adsorbed film and the excess Gibbs energy of adsorption $ {\widehat{g}}^{\mathrm{H},\mathrm{E}} $ were evaluated from thermodynamic analysis of surface tensions for the 1-decyl-3-methylimidazoulium bromide (C10mimBr)–tetraethylene glycol monooctyl ether (C8E4) and 1-decyl-3-methyl-imidazolium tetrafluorobrorate (C10mimBF4)–C8E4 systems, where the counter anion of imidazolium salts is different from each other. The higher miscibility of two components compared to an ideal mixing and thus negative $ {\widehat{g}}^{\mathrm{H},\mathrm{E}} $ were observed in the former, which comes from the ion–dipole interaction between imidazolium cation and the oxyethylene group of C8E4. On the other hand, the lower miscibility and thus positive $ {\widehat{g}}^{\mathrm{H},\mathrm{E}} $ were observed for the latter. Such differences were attributed to that BF4 ? forms two hydrogen bonds and has stronger affinity with the cationic head group of C10mim+ than Br?. This results in that the ion–dipole interaction between C8E4 and C10mim+ cation is diminished in the C10mimBF4–C8E4 system. 相似文献