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31.
Akiko Saito Mana Emoto Akira Tanaka Yuki Doi Kazuaki Shoji Yoshiyuki Mizushina Hiroshi Ikawa Hiromi Yoshida Nobuyasu Matsuura Noriyuki Nakajima 《Tetrahedron》2004,60(52):12043-12049
A simple method for the synthesis of procyanidin B3 substituted with a galloyl group at the 3 and 3″ position is described. Condensation of a benzylated catechin-3-O-gallate electrophile with a nucleophile, catechin and catechin-3-O-gallate, proceeded smoothly and stereoselectively to afford the corresponding dimer gallates, procyanidin B3-3-O-gallate and procyanidin B3-3,3″-di-O-gallate, in good yields. Further, their antioxidant activities on UV-induced lipid peroxide formation, DPPH radical scavenging activity and inhibitory activity of DNA polymerase were also investigated. Among three procyanidin B3 congeners (procyanidin B3, 3-O-gallate and 3,3″-di-O-gallate), the 3,3″-di-O-gallate derivative showed the strongest antioxidant and radical scavenging activity. Interestingly, the 3-O-gallate derivative was the strongest inhibitor of mammalian DNA polymerase with IC50 value of 0.26 μM, although it showed the weakest antioxidant and radical scavenging activity. It became apparent that the presence of a galloyl group at the C-3 position in the proanthocyanidin oligomer was very important for biological activity, however, the antioxidant activity of these compounds was not parallel to the DNA polymerase inhibitory activity. 相似文献
32.
Sotoyama W Satoh T Sato H Matsuura A Sawatari N 《The journal of physical chemistry. A》2005,109(43):9760-9766
The absorption and emission spectra of the Pt(II) complexes containing N wedge C wedge N-coordinating tridentate ligands, platinum(II) 1,3-di(2-pyridyl)benzene chloride [Pt(dpb)Cl] and platinum(II) 3,5-di(2-pyridyl)toluene chloride [Pt(dpt)Cl], together with their corresponding free ligands, 1,3-di(2-pyridyl)benzene (dpbH) and 3,5-di(2-pyridyl)toluene (dptH), have been analyzed by density functional theory (DFT) for the ground state and time-dependent DFT (TDDFT) for the excited states. T(1)(A(1)) and S(1)(B(2)) of the complexes (in C(2)(v) symmetry) were assigned on the basis of the calculated excitation energies as well as comparison of the experimental spectroscopic properties and the calculated states' characteristics. The calculated excitation energies for T(1) and S(1) of the complexes as well as those for T(1) of the free ligands were in good agreement with their observed values within 600 cm(-1). The d-pi* characters of the excited states were evaluated from the change in electron densities between the ground and excited states by Mulliken population analysis; values of 25% for T(1) and 32% for S(1) were obtained for both complexes. The calculated values of d-pi* character were found to be consistent with the reported emission lifetimes as well as the observed emission energy shifts from the corresponding free ligands. Most spectroscopic properties of the complexes and the free ligands, which include solvatochromic shift, Stokes shifts, methyl substitution shifts, and emission spectra profiles, were well explained from the calculation results. 相似文献
33.
Hideko Koshima Teruo Matsuura 《Journal of photochemistry and photobiology. A, Chemistry》1996,100(1-3):85-91
This paper deals with the solid state bimolecular photoreactions occurring at the interface between crystallites of two different organic compounds prepared as a polycrystalline mixture by melting-resolidification. The photoreactions include the photoaddition of NH compounds to aromatic and olefinic double bonds, hydrogen abstraction, condensation reaction via photoelectron transfer and [2+2] photoaddition. Particular attention is focused on the characterization of the polycrystalline mixture, the selectivity of the photoreactions in the solid state compared with those in the solution phase and the factors controlling the photoreactions. 相似文献
34.
Speciation of mercury in salmon egg cell cytoplasm was investigated by surfactant-mediated high-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC/ICP-MS), where an ODS (octadecylsilica) column coated with a bile acid derivative, CHAPS (3-[(3-cholamidopropyl)-dimethylammonio]-1-propane sulfonate), was used for species separation. Prior to the speciation analysis, total Hg in the cell cytoplasm was determined by ICP-MS at m/z 202 in a flow injection mode. For the precise measurement, salmon egg cell cytoplasm was diluted five-fold with 0.1 M Tris (Tris(hydroxymethyl)aminomethane)-HNO3 buffer solution, and the standard addition method was employed. Thus, the total concentration of Hg in cell cytoplasm was estimated to be 12.4 ng g−1 on the wet weight basis. Next, the cell cytoplasm diluted five-fold with 0.1 M Tris-HNO3 buffer solution was analyzed by surfactant-mediated HPLC with the dual detection system of a UV absorption detector and an ICP-MS instrument. Two peaks corresponding to some proteins and small molecules were mainly observed in those chromatograms. When salmon egg cell cytoplasm was diluted five-fold with 0.01 M Tris buffer solution or pure water, some precipitates appeared probably because of precipitation of hydrophobic proteins in cytoplasm. After the precipitates were eliminated with a membrane filter, the filtrate was subjected to the analysis by surfactant-mediated HPLC/UV/ICP-MS. As a result, the peaks for small molecular species of Hg were clearly observed at the retention time near 4.0 min (corresponding to low-molecular weight zone) in the chromatograms with UV absorption detection as well as with Hg- and S-specific ICP-MS detections. The small molecule bound with Hg was identified as cysteine through the cysteine-spiked experiment. In addition, the protein fraction on the chromatogram obtained by using the CHAPS-coated ODS column was further analyzed by SEC (size exclusion chromatography). Consequently, several protein peaks with molecular weight of 300, 50 and 12 kDa were observed in all the detections of UV absorption, Hg and Se, although two peaks among them were coincident in the case of S. These results indicate that Hg in salmon egg cell cytoplasm binds with proteins containing selenocysteine and/or cysteine residues in proteins. 相似文献
35.
Akira Nishinaga Toshio Itahara Tadashi Shimizu Haruo Tomita Kanji Nishizawa Teruo Matsuura 《Photochemistry and photobiology》1978,28(4-5):687-692
Abstract— The mechanisms by which 4-substituted 2,6-di- t -butylphenols are oxygenated by base- and Co(II) Schiff base complex-catalysis into o - or p -peroxyquinols and their Co(III) complexes, respectively, have been investigated. For the base-catalyzed oxygenation, a one-step ionic mechanism involving no radical species is suggested to be the most probable one. For the formation of the peroxycobalt(III) complexes, the following stoichiometry is concluded: ArOH + Co(II) + 5/4 O2 → peroxycobalt(III) complex + 1/2 H2 O. A mechanism involving an electron transfer between the phenols and the Co(II)-O2 complex followed by further electron transfer between the formed phenoxy radicals and the Co(II) complex to give the corresponding phenolate anions is proposed. 相似文献
36.
Poly(1,4-dimethyl-6-vinylnaphthalene) and poly(1,2,4-trimethyl-6-vinylnaphthalene) react with singlet oxygen to give corresponding endoperoxide polymers which on warming generate singlet oxygen efficiently. Singlet oxygenations by the use of these polymers have been described. 相似文献
37.
Matsuura K Hibino M Ikeda T Yamada Y Kobayashi K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(2):352-359
We describe herein the relationship between the spatial arrangement of self-organized galactose clusters and lectin recognition. beta-Galactose-modified deoxyuridine phosphoramidite was synthesized and applied to solid-phase synthesis to provide 18-, 20-, and 22-mers of site-specifically galactosylated oligodeoxynucleotides (Gal-ODNs). These Gal-ODNs were self-organized through hybridization with the corresponding 18-, 20-, and 22-mers of half-sliding complementary ODNs (hsc-ODNs) to give periodic galactoside clusters. The self-organization of ODNs was confirmed by size exclusion chromatography and gel electrophoresis. The binding of the Gal-clusters to the FITC-labeled RCA(120) lectin was analyzed by monitoring the change in fluorescence intensity. The assembly of 20-mer Gal-ODN with the 20-mer hsc-ODN was strongly and cooperatively recognized by the lectin. The 18-mer assembly was bound more weakly and less cooperatively, and the 22-mer assembly was minimally bound to the lectin. RCA(120) lectin recognized not only the density of galactoside residues, but also the spatial arrangement. The size of the Gal cluster was estimated from the association constant of Gal-ODN with hsc-ODN. The relationship between lectin-recognition and Gal-cluster size is also discussed. 相似文献
38.
Hiroatsu Matsuura Yoshiyuki Kawashima Chiaki Hirose 《Journal of Molecular Structure》1974,20(2):205-212
The rotational constant B and the l-type doubling constant q were determined for the v5, v3+v6 and v2, states of CH2I from the microwave transition frequencies, in combination with the infrared data previously reported. Since these vibrational states were coupled through the Fermi resonance and the xy-type E-E and A1-E Coriolis resonances, the analysis was made by setting up and solving the complete form of the secular determinants of the energy matrices. The rotational and l-type doubling constants were determined as B5, = 0.250 173 cm?1, B36 = 0.247 600 cm?1, B2 = 0.249 369 cm?1, q5 = ?0.000 027 cm?1 and q36 = ?0.000 179 cm?1, which are unperturbed by Fermi and Coriolis interactions. Other band constants for v5 and v3+v6 were also refined in accordance with the new values of B5 and B36. The present study indicated that the combined analysis of microwave and infrared spectral data was useful for the precise determination of vibration-rotation, levels in the perturbed system. 相似文献
39.
Matin MR Katsumoto Y Matsuura H Ohno K 《The journal of physical chemistry. B》2005,109(42):19704-19710
Hydration of short-chain poly(oxyethylene)s, CH(3)(OCH(2)CH(2))(m)OCH(3) (abbreviated as C(1)E(m)()C(1)) (m = 1-3), in carbon tetrachloride has been studied by infrared spectroscopy. The O-H stretching vibrations of water in ternary solutions with H(2)O:C(1)E(m)C(1):CCl(4) mole ratios of 0.000418:0.005:0.995 to 0.000403:0.04:0.96 were analyzed. Two types of hydrogen bonds are formed in the interaction between water and C(1)E(m)C(1) in carbon tetrachloride; one is a monodentate hydrogen bond, in which only one of the O-H bonds of a water molecule participates in hydrogen bonding, and the other is a bidentate hydrogen bond, in which both of the O-H bonds of a water molecule participate in hydrogen bonding by bridging oxygen atoms separated by two or more monomer units on the polymer chain. An important finding is that the bidentate hydrogen-bond bridge is not formed between the nearest-neighbor oxygen atoms. This experimental observation supports the results of previous molecular dynamics simulations. The shortest oligomer of poly(oxyethylene), i.e., CH(3)OCH(2)CH(2)OCH(3) (1,2-dimethoxyethane) with a single monomer unit, is suggested not to be an adequate model for this polymer with respect to hydrogen bonding to water. The hydrogen bonding in a 1:1 C(1)E(m)C(1)-water adduct in carbon tetrachloride represents primitive incipient hydration of poly(oxyethylene). The present results indicate that both monodentate and bidentate hydrogen bonds are important and the latter is destabilized more rapidly than the former with increasing temperature. This dehydration process can be a potential mechanism of the poly(oxyethylene)-water phase separation. 相似文献
40.
Akio Kamimura Rie MoritaKenji Matsuura Hiromasa MitsuderaMasashi Shirai 《Tetrahedron》2003,59(50):9931-9938
A convenient stereoselective synthesis of β-lactams from thio-Michael/aldol tandem adduct is described. syn-Selective tandem reaction followed by amidation and intramolecular SN2 reaction provided β-lactams in diastereomerically pure form. The tandem reaction with aliphatic aldehydes, on the other hand, afforded a mixture of diastereomers of corresponding tandem adducts in about 3:1 ratio so that the conversion to β-lactams afforded a diastereomeric mixture. As an alternative approach to prepare the tandem adducts, the stereoselective Michael addition of aliphatic thiols to Baylis-Hillman adduct was developed. The stereoselectivity was sensitive to the protective group at the hydroxyl group and TBS protection brought the most successful syn-selective formation of the tandem adducts. The procedure could be applied to the ketone derivatives of the Baylis-Hillman adduct but no selectivity was observed for the nitrile-Baylis-Hillman adducts. A similar conversion of the adduct provided desired β-lactams stereoselectively. 相似文献