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71.
72.
K. Dimroth A. Berndt F. Br A. Schweig R. Volland 《Angewandte Chemie (International ed. in English)》1967,6(1):34-40
The distribution of the unpaired electron over the oxygen and the 24 carbon atoms in the free 2,4,6-triphenylphenoxy radical was determined by electron spin resonance spectroscopy and quantum-mechanical approximation methods. The hyperfine splitting was evaluated with the aid of the spectra of triphenylphenoxyls deuterated in some or all of the substituent phenyl groups. The results of the quantum-mechanical approximations were checked by recording the ESR spectra of triphenylphenoxyls labeled with 13C in positions 1,2,3, or 4 of the central ring. The spin density distribution permits a first discussion of the 17O-coupling constants of correspondingly labeled triphenylphenoxyl and other organic free radicals. 相似文献
73.
J. C. Evans K. R. N. Rao S. K. Jackson C. C. Rowlands M. D. Barratt 《Journal of separation science》1985,8(12):829-830
Radicals generated in linoleic acid and deuterated linoleic acid have been trapped by the spin trap 2-methyl-2-nitroso-propane (MNP) and identified by electron spin resonance (ESR) and ENDOR spectroscopy. The formation of two distinct secondary alkyl radical adducts (one conjugated, the other non-conjugated, as shown by their UV absorption spectra) was demonstrated by 11, 11-dideuterio-9-cis-12-cis-linoleic acid using HPLC and ESR spectroscopy. 相似文献
74.
The stability of spontaneous thin layers and thin layers formed upon cathodical polarization of Ti in KOH solutions have been
studied by potentiostatic and ellipsometric methods. At open circuit potential (OCP) the strongly adherent films, whose thickness
depends on the concentration of the KOH solution, were formed. During the cathodic polarization the transformation of these
films to weakly adsorbed precipitated layers on the electrode surface was observed. Comparing the theoretically computed curves
with the experimental Ψ vs Δ loci measured ellipsometrically, the complex indices of refraction and the thickness of the generated films, from 3.6
to 60 nm in 1 M KOH and from 36 to 105 nm in 5 M KOH (adherent to the electrode surface), were determined. At OCP the rate
of film growth increases with increasing the concentration of KOH solution. Cathodic polarizations change the chemical composition
and retard the rate of film growth. Based on the ellipsometric and electrochemical data the chemical compositions of the formed
films consisted of TiO2, Ti2O3, TiO2·H2O, Ti(OH)3 and TiOOH·nH2O. 相似文献
75.
It is well known that porphyrin derivatives play a key role in the primary process of photo-synthesis[1], in which porphyrins directly absorb the sunlight or indirectly acquire excitation en-ergy from light-harvesting antenna system to reach their excited state, and then donate electrons to quinone acceptors to yield a series of charge-separated species. In general, only first singlet ex-cited state of porphyrins is involved in energy transfer process[2]. However, highly excited state (S2 stat… 相似文献
76.
New spin-state-selective (S3) NMR pulse sequences exclusively applying cross-polarization schemes to achieve optimum homonuclear and heteronuclear 1H-X coherence transfer are reported for the simple and accurate measurement of the magnitude and sign of heteronuclear coupling constants for samples at natural abundance. The proposed spin-edited HCP-TOCSY experiments are based on clean heteronuclear S3 excitation, generated by simultaneous co-addition of two independent in-phase and anti-phase components created during the mixing heteronuclear J-cross-polarization (HCP) step, which is finally transferred to other protons by a conventional homonuclear TOCSY mechanism. Selective 1D and non-selective 2D approaches for the easy determination of long-range proton-carbon and proton-nitrogen coupling constants on any protonated and non-protonated heteronuclei are presented and discussed for several organic molecules. 相似文献
77.
E.?V.?TsipisEmail author V.?V.?Kharton I.?A.?Bashmakov E.?N.?Naumovich J.?R.?Frade 《Journal of Solid State Electrochemistry》2004,8(9):674-680
Developments of intermediate-temperature solid oxide fuel cells (IT SOFCs) require novel anode materials with a high electrochemical activity at 800–1070 K. The polarization of cermet anodes, made of nickel, ceria and yttria-stabilized zirconia (YSZ) and applied onto a YSZ solid electrolyte, can be significantly reduced by catalytically active ceria additions, the relative role of which increases with decreasing temperature. Further improvement is observed when using Ce0.8Gd0.2O2–
(CGO) having a high oxygen ionic conductivity instead of undoped ceria, owing to enlargement of the electrochemical reaction zone. Nanocrystalline CGO powders with grain sizes of 8–35 nm were thus synthesized via the cellulose-precursor technique and introduced into Ni–CGO–YSZ cermets, and tested in contact with a (La0.9Sr0.1)0.98Ga0.8Mg0.2O3–
(LSGM) electrolyte at 873–1073 K. The results showed that the anode performance can be enhanced by additional surface activation, in particular by impregnation with a Ce-containing solution, and also by incorporation of YSZ, which probably acts as a cermet-stabilizing component. The overpotential of the surface-modified Ni–CGO (25 wt%–75 wt%) anode in a 10% H2/90% N2 atmosphere was approximately 110 mV at 1073 K with a current density of 200 mA/cm2.Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003 相似文献
78.
Molecular mobility in thermotropic polyesters and side-chain polymers with different struc-ture of mesogens and spacers has been studied by dielectrical method in dilutesolutions. The results made it possible to establish the multiplicity of dielectric relaxationtransitions which reflects the small- and large-scale types of molecular motion. It was shownthat dielectric relaxation processes occurring in accordance with local mechanism (relaxationtimes 10~(-9)--10~(-7)s. and the activation energy 10--50kJ/mol) are due to the mobility of kineticchain elements of different length within a monomer units. It was found that the dielectricrelaxation process connected with a large-scale form of molecular motion (relaxation times10~(-5)--10~(-6)s. and the activation energy 100kJ/mol) did not depend on the molecular massbut was infiuenced by factors changing the conformational state of the macromolecule. It isestablished tha the cooperative reorientation mobility of associated mesogenic fragments isthe source of the large-scale process. 相似文献
79.
Summary. A formalism has been developed that describes spin crossover equilibrium in the solid state by taking into account the effects
of n nearest neighbours of a given molecule on its partition function. In this way binary and many-body interactions of the order
n + 1 are included into the theoretical model and represented by non-ideality parameters connected with the splitting of free
energy levels. Binary interactions are characterised by the main splittings whereas higher order interactions manifest themselves
in asymmetries of splittings within multiplets. The contribution of molecular interactions can also be written in terms of
formal excess free energies of the second, third, fourth and higher orders. Simple relationships between excess free energies
and parameters of multiplets have been found for binary, ternary and quaternary interactions. This formalism is reduced to
that of the model of binary interactions when effects of surroundings are additive leading to equidistant free energy multiplets.
Higher order interactions may cause an abrupt spin crossover but in a limited range of compositions around the transition
point. The regression of experimental transition curves of one-step spin crossover may yield estimates of excess energies
up to the fifth order. 相似文献
80.
The mechanism for nitrogen activation by molybdenum complexes is a complicated one, involving as it does the coupling of a quartet molybdenum reactant with a singlet nitrogen molecule, passing via a series of quartet and doublet encounter complexes to a triplet intermediate, with the subsequent spin crossing to the singlet surface which then leads via a singlet transition state to the final pair of singlet products. We have investigated in detail a variety of levels of theory to describe the crossing of these electronic surfaces and have calculated both lower-bound and actual minimum energy crossing points for the key spin inversion processes. 相似文献