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151.
A kinetic and thermodynamic investigation on the antioxidant activity of 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (2), 2,2'-ethylidenebis(4,6-di-tert-butylphenol) (3), and 4,4'-methylenebis(2,6-di-tert-butylphenol) (4) are reported. EPR studies of the equilibration between 3 or 4 and a reference phenol, and the corresponding phenoxyl radicals, allowed us to determine the O-H bond dissociation enthalpy (BDE) of the O-H bond as 81.2 and 81.1 kcal/mol in 3 and 4, respectively. Despite this similarity, the absolute rate constants for the reaction with peroxyl radicals, determined by autoxidation studies under controlled conditions, indicate that the o-bisphenols 2 and 3 behave as excellent antioxidants while the p-bisphenol 4 is less effective by a factor of 64 and 22, respectively. FT-IR spectroscopy and product studies suggest that the very good antioxidant activity of the o-bisphenols largely arises from both the reduced steric crowding about the hydroxyl group and the stabilization of the aroxyl radical due to the formation of an intramolecular hydrogen bond between the residual OH and the oxygen radical center. 相似文献
152.
The crystal structure of an inorganic linear polymer consisting of Mn(II) and an N-centered tripodal ligand N,N-bis(2-(6-methyl)pyridylmethyl)glycinate is presented (1, C(16)H(20)N(3)O(3)F(6)P(1)Mn(1), a = 9.993(2) A, b = 13.285(3) A, c = 16.040(3) A, orthorhombic, Pnam, Z = 4). The polymeric structure is ensured by carboxylato ligands connecting two Mn(II) in a rather rare syn-anti geometry. The magnetic properties of this infinite chain have been investigated, together with the magnetic properties of a dimeric Mn(II) compound (3) from a closely related ligand [N,N-bis[(1-methylimidazol-2-yl)-methyl)glycinate] involving an unusual bis(monatomic-carboxylato) bridge. The inorganic polymer 1 shows a pseudo-2D magnetic structure, with a major interaction pathway along the chain (J/k = -0.172 +/- 0.005 K) and an interchain minor one (zJ'/k = -0.006 +/- 0.004 K). These properties are reminiscent of those from a closely related previously reported inorganic Mn(II) polymer (2 obtained from manganese(II) and N,N-(2-pyridylmethyl)((1-methylimidazol-2-yl)methyl)glycinate). The dimer 3 shows a small antiferromagnetic coupling of J/k = -0.693 +/- 0.016 K. To address the influence of the carboxylato bridging mode on the magnetic properties, these complexes are compared to a series of compounds involving carboxylato bridges of several geometries between Mn(II) ions. Carboxylato bridges induce usually antiferromagnetic coupling, with the magnitude of the interaction (/J/) increasing with the number of bridges. The J value is dependent on the bridging mode. The syn-syn bridge is an efficient pathway, even by comparison with the monatomic [(mu-eta(1)-carboxylato)] bridge. 相似文献
153.
Baldini M Belicchi-Ferrari M Bisceglie F Pelosi G Pinelli S Tarasconi P 《Inorganic chemistry》2003,42(6):2049-2055
Two new 5-formyluracil thiosemicarbazone (H(3)ut) derivatives, Me-H(3)ut (1) and Me(2)-H(3)ut (2), were synthesized by reacting thiosemicarbazides, mono- and dimethylated on the aminic nitrogen, with 5-formyluracil and were subsequently characterized. These ligands, treated with copper chloride and nitrate, afforded three complexes: [Cu(Me-H(3)ut)Cl(2)].H(2)O (3), [Cu(Me(2)-H(3)ut)Cl(2)].H(2)O (4), and [Cu(Me-H(3)ut)(NO(3))(OH(2))(2)]NO(3) (5). The crystal structures of these complexes have been determined by single-crystal X-ray diffraction. In 3 and 4, a similar pentacoordination is present; the copper atom is surrounded by the ligand SNO donor atoms and by two chloride ions. The structure of 5 consists of [Cu(Me-H(3)ut)(NO(3))(OH(2))(2)](+) cations and nitrate anions. The copper coordination (4 + 2) involves the SNO ligand atoms and a water oxygen in the basal plane; the apical positions are occupied by a second water oxygen and by an oxygen of a monodentate nitrate group. Two biochemical techniques, namely DNA titration in the UV-vis region and thermal denaturation, have been employed to probe the details of DNA binding of these compounds. Analysis of the results suggests that our compounds are able to interact with DNA by electrostatic and groove binding but not by intercalation. The compounds have been also tested in vitro on human leukemic cell line U937, but they are not able to inhibit significantly cell proliferation. 相似文献
154.
155.
Davide Franco 《Geometriae Dedicata》2000,81(1-3):33-52
Extending a result of Manivel, we prove the following: THEOREM. Suppose $\sum\limits_i {b_i \geqslant } \sum\limits_i {a_i } + n$ and $$\sum\limits_i {b_i } [n + d_i d_i - 1] \geqslant \sum\limits_i {a_i } [n + l_i l_i - 1] + n.$$ Then the kernel E(d) of the general morphism: $$\mathop \oplus \limits_{i = 1}^v (Bi \otimes O_{P^n } (d_i )) \to \mathop \oplus \limits_{j = 1}^v (A_j \otimes O_{P^n } (l_i ))$$ (l 1>...>l s>d 1>...>d v) is a globally generated vector bundle, except for at most finitely many sets $\left\{ {b_i ,a_i } \right\}$ . 相似文献
156.
157.
J. V. Pinto M. M. Cruz R. C. da Silva N. Franco A. Casaca E. Alves M. Godinho 《The European Physical Journal B - Condensed Matter and Complex Systems》2007,55(3):253-260
The magnetic and electrical properties of Co-implanted
single crystalline TiO2 rutile are presented. For fluences of
the order of 1017 cm-2 and implantation energy of 150
keV the maximum atomic concentration of cobalt is 13 at% at a depth
of 65 nm from the surface. The as implanted single crystals exhibit
superparamagnetic behaviour attributed to the formation of nanosized
cobalt clusters. After annealing at 1073 K an anisotropic
ferromagnetic behaviour emerges with the easy magnetization axis
lying in the (001) plane of rutile. The ferromagnetic behaviour is
associated with oriented cobalt aggregates. Electrical conductivity
of the implanted samples annealed in vacuum also exhibits
anisotropic behaviour at low temperatures, but no magnetoresistive
effects were detected. 相似文献
158.
Entangled two-photon generalized binomial states of the electromagnetic field in two separate cavities are considered. The
nonlocal properties of this entangled field state are analyzed by studying the electric field correlations between the two
cavities. A Bell’s inequality violation is obtained using an appropriate dichotomic cavity operator that is, in principle,
measurable.
The text was submitted by the authors in English. 相似文献
159.
Giovanna Bruni Vittorio Berbenni Franco Sartor Chiara Milanese Alessandro Girella Dionigio Franchi Amedeo Marini 《Journal of Thermal Analysis and Calorimetry》2012,108(1):235-241
In this work, thermoanalytical, diffractometry, and microscopy measurements have been performed in order to characterize the
effect of high energy milling on a drug active in the migraine prophylaxis and smoke cessation. We can assert that the mechanical
treatment induces only a partial amorphisation of the solid phase, in particular it reduces the crystal order by producing
lattice defects which propagate from the surface to the bulk crystal. For this reason, the DSC is able to detect the presence
of ordered solid, while the powder X-ray diffractometry, because of its low penetration depth, does not reach the crystalline
core of the particles. 相似文献
160.
An infinite-parameter family of discontinuous area-preserving maps is studied, using geometrical methods. Necessary and sufficient conditions are determined for the existence of some bounding invariant sets, which guarantee global stability. It is shown that under some additional constraints, all orbits become periodic, most of them Lyapounov stable, and with a maximal period in any bounded domain of phase space. This yields a class of maps acting on a discrete phase space. 相似文献