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61.
Piotr Dobrzynski 《Journal of polymer science. Part A, Polymer chemistry》2004,42(8):1886-1900
Lactide polymerization using zirconium(IV) acetylacetonate [Zr(acac)4] as an initiator was investigated. In the reaction between Zr(acac)4 and the monomer molecule, lactide deprotonation and the release of acetylacetone occurred. The structures of the obtained complexes were analyzed with high‐resolution NMR spectroscopy. A computational method was used to calculate the hypothetical structures. The role of the obtained complexes in the initiation of polymerization and the reaction of chain growth was proposed. The influence of the reaction temperature on the structures of the complexes was investigated. Polylactide chain growth proceeded by an insertion‐coordination mechanism. The polymer chain grew on one ligand, which was formed in advance from a deprotonated lactide. The molecular masses of the obtained polymers were the same as the theoretical masses and were directly proportional to the reaction conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1886–1900, 2004 相似文献
62.
E. M. Glebov V. P. Grivin V. F. Plyusnin A. V. Udaltsov 《Journal of Structural Chemistry》2006,47(3):476-483
Interaction between MnCl2 and diethylamine (DEA) in aqueous solutions has been studied by UV, IR, and EPR spectroscopy as part of the design and research program on models of natural photosystems. The composition of the precipitate for comparable concentrations of reagents and solute oxygen has been investigated. Mn(II) was found to be oxidized with oxygen to give MnO2·H2O as a precipitate. In the solution over the precipitate, Mn(III) complexes with DEA are formed; the complex molecule has four and six amine molecules in the coordination sphere. 相似文献
63.
V.V. Glushkov S.V. Demishev M.I. Ignatov Yu.B. Paderno N.Yu. Shitsevalova O.A. Churkin N.E. Sluchanko 《Journal of solid state chemistry》2006,179(9):2871-2874
In order to reveal the nature of the ground state of archetypal intermediate-valence compound SmB6, a comprehensive study of its transport and magnetic properties was carried out on high-quality single crystals at temperatures of 1.8-300 K in magnetic fields up to 7 T. A drastic enhancement of negative magnetoresistance was observed below 14 K, with the maximum absolute value of Δρ/ρB2∼2.2×10−3 T−2 at T≈5.2 K. This effect seems to be attributable to anomalous magnetic scattering of many-body (exciton-polaronic) complexes induced by fast valence fluctuations on Sm sites. The observed anomalies of magnetotransport, thermoelectric and magnetic characteristics are discussed in terms of electron phase transition to the coherent state of interacting many-body complexes occurring at T*∼5 K. 相似文献
64.
New Schiff bases of 2,4‐dihydroxybenzaldehyde with siloxane‐α,ω‐diamines having different numbers of siloxane units in the chain have been synthesized and characterized by spectroscopy, elemental and thermal analyses. These azomethines were found to form complexes readily with copper(II), nickel(II), cobalt(II), cadmium(II) and zinc(II). From IR and UV–Vis studies, the phenolic oxygen and imine nitrogen of the ligand were found to be the coordination sites. Thermogravimetric analysis (TGA) data indicate the chelates to be more stable than the corresponding ligands. The melting points increase with shortening of the siloxane segment from azomethine, as well as the result of complexation. The chelates obtained were covalently inserted in polymeric linear structures by polycondensation through the OH‐difunctionalized ligand with 1,3‐bis(carboxypropyl)tetramethyldisiloxane. Direct polycondensation, assisted either by acetic anhydride or N,N′‐dicyclohexylcarbodiimide as dehydrating agent and the complex 4‐(dimethylamino)pyridinium 4‐toluenesulfonate as catalyst, was used for the synthesis of these compound types. The structures of the polymers obtained were confirmed by IR, UV and 1H NMR. Characterization was undertaken by TGA, solubility tests and viscosity measurements. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
65.
An O-bonded sulphito complex, Rh(OH2)5(OSO2H)2+, is reversibly formed in the stoppedflow time scale when Rh(OH2)
6
3+
and SO2/HSO
3
−
buffer (1 <pH< 3) are allowed to react. For Rh(OH2)5OH2++ SO2 □ Rh(OH2)5(OSO2H)2+ (k1/k-1), k1 = (2.2 ±0.2) × 103 dm3 mol−1 s−1, k−1 = 0.58 ±0.16 s−1 (25°C,I = 0.5 mol dm−3). The protonated O-sulphito complex is a moderate acid (K
d
= 3 × 10−4 mol dm−3, 25°C, I= 0.5 mol dm−3). This complex undergoes (O, O) chelation by the bound bisulphite withk= 1.4 × 10−3 s−1 (31°C) to Rh(OH2)4(O2SO)+ and the chelated sulphito complex takes up another HSO
3
−
in a fast equilibrium step to yield Rh(OH2)3(O2SO)(OSO2H) which further undergoes intramolecular ligand isomerisation to the S-bonded sulphito complex: Rh(OH2)3(O2SO)(OSO2)- → Rh(OH2)3(O2SO)(SO3)− (k
iso
= 3 × 10−4 s−1, 31°C). A dinuclear (μ-O, O) sulphite-bridged complex, Na4[Rh2(μ-OH)2(OH)2(μ-OS(O)O)(O2SO)(SO3) (OH2)]5H2O with (O, O) chelated and S-bonded sulphites has been isolated and characterized. This complex is sparingly soluble in water
and most organic solvents and very stable to acid-catalysed decomposition 相似文献
66.
Dávid Szegvári Romána Zelkó Péter Horváth András Gergely 《Journal of inclusion phenomena and macrocyclic chemistry》2007,57(1-4):169-172
Enantioselective solubility of rac-norgestrel was found in the presence of γ-cyclodextrin or hydroxypropyl-γ-cyclodextrin.
In both cases the efficacious enantiomer was dissolved in greater extent. Calculating the molar absorptivity and molar ellipticity
spectra of the γ- and hydroxypropyl-γ-cyclodextrin aqueous complexes, a simple and rapid direct circular dichroism (CD) spectrometric
method was obtained for the determination of the enantiomer ratio in aqueous solutions. 相似文献
67.
68.
Hui Zhang 《Journal of solid state chemistry》2004,177(3):772-780
A nano-scale magnetic solid base catalyst MgAl-OH-LDH/MgFe2O4 (where LDH denotes layered double hydroxide) composed of MgAl-OH-LDH Brønsted base catalytic layers coated on MgFe2O4 spinel cores has been prepared. A magnetic precursor MgAl-CO3-LDH/MgFe2O4 was prepared by a method involving separate nucleation and aging steps, and subsequently calcined to give a mixed metal oxide composite MgAl(O)/MgFe2O4 which was rehydrated to give MgAl-OH-LDH/MgFe2O4. The structure and magnetic properties of the nano-scale magnetic solid base MgAl-OH-LDH/MgFe2O4, together with those of the magnetic precursor MgAl-CO3-LDH/MgFe2O4 and MgFe2O4 were characterized by XRD, XPS, low temperature N2 adsorption and vibrating sample magnetometry (VSM). The MgAl-OH-LDH/MgFe2O4 composite possesses a mesoporous structure with pore size ranging from 2 to 20 nm with particle size mainly in the range 35-130 nm. The catalytic properties of MgAl-OH-LDH/MgFe2O4 were evaluated using the self-condensation of acetone at 273 K as a probe reaction. The results showed that the conversion of acetone to diacetone alcohol reached the thermodynamic equilibrium value of 23% at 273 K. The catalyst was easily recovered through application of an external magnetic field, and when the reclaimed catalyst was used in a second run for the same reaction, the reactivity remained unchanged. 相似文献
69.
Investigation on ultrafast thrid—order optical nonlinearity of metal(dmit)2/mnt)2 Charge transfer complexes 下载免费PDF全文
We have investigated the transient third-order optical nonlinearity of the solutions of Metal(dmit)2/(mnt)2 salts in acetone by employing femtosecond optical Kerr gate measurement at 830nm wavelength.An order of enhancement on the second-order hyperppolarizability is found for the above salts with central atoms of Cu and Ni.We have suggested an explanation for the enhancement based on the extension of electronic conjugation by the entring Cu or Ni atom. 相似文献
70.
Jean-Marc Kern Jean-Pierre Sauvage Gerard Bidan Bernadette Divisia-Blohorn 《Journal of polymer science. Part A, Polymer chemistry》2003,41(22):3470-3477
This article provides an overview of the fundamental principles of the synthesis of metallocatenanes and metallorotaxanes. It also describes the synthesis and properties of electronic conducting polymers—polypyrrole and polythiophene—built around metallocatenanes and metallorotaxanes. The particular properties of this new class of polymers, including the possibility of transmetallation reactions being performed with them and the observation of electronic coupling between the metal centers and the conducting matrix, are discussed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3470–3477, 2003 相似文献