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151.
Jan S. Jaworski 《Monatshefte für Chemie / Chemical Monthly》1984,115(4):415-418
A two parameter approach to solvent variations in the electroreduction rate constants of cobalt complexes and europium cations is presented and discussed in terms of solvent—solute and solvent—solvent interactions.
Ein Zwei-Parameter Donor-Acceptor-Ansatz für Lösungsmitteleffekte bei der Elektrodenkinetik von Kationen (Kurze Mitteilung)
Zusammenfassung Es wird eine Zwei-Parameter-Annäherung der Lösungsmitteleinflüsse auf die Geschwindigkeitskonstanten der Elektroreduktion von Kobalt-Komplexen und Europium-Kationen präsentiert und auf der Basis von Lösungsmittel—gelöster Stoff- und Lösungsmittel—Lösungsmittel-Wechselwirkung diskutiert.相似文献
152.
One-dimensional magnetism and crystal structure ofcatena-di-bromobis(3,5-dimethylpyridine)copper(II)
Johannes A. C. van Ooijen Jan Reedijk Eduard J. Sonneveld Jan W. Visser 《Transition Metal Chemistry》1979,4(5):305-307
Summary Crystals ofcatena-di--bromobis(3,5-dimethylpyridine)copper(II) are monoclinic, space group P21/a. The unit cell constants area=13.900(2),b=14.416(2),c=4.097(1) Å,=93.49(2)°, V=819.4 Å3 and Z=2. The structure was determined from powder data using a Guinier-Johansson focussing powder camera. The structure was solved using a simplex method for function minimization to a conventional R-value of 0.13.The structure consists of infinite linear chains parallel toc in which the copper coordination is distorted elongated octahedral. Cu-Br distances were found to be 2.449(7) and 3.286(7) Å, whereas the Cu-N bond length is 2.02(2) Å. All distances are in the range usually observed for this type of compounds.The antiferromagnetic superexchange interactions between adjacent CuII ions (J = –21 cm–1) has been compared with those observed in structural similar CuBr2L2 compounds. The differences in observed J-values are discussed briefly, in relation to the structural variations. It appears that very small changes in structural parameters strongly affect the magnetic exchange. 相似文献
153.
The sorption of solvent vapours onto dried cellulose has been investigated. The time-dependence and the effect of the solvent-water ratio is discussed. The studies concerned the properties of methanol, ethanol, propanol and butanol. 相似文献
154.
155.
Sherif El-Basil Gani Jashari Jan V. Knop Nenad Trinajstić 《Monatshefte für Chemie / Chemical Monthly》1984,115(11):1299-1312
The reduced graph model, when used in conjunction with the search trees method, provides a novel combinatorial procedure for the enumeration and generation ofKekulé structures. The procedure is suited for large benzenoid hydrocarbons consisting of cata- and thin peri-condensed parts.
Zur Anwendung des Reduced Graph Model im Zusammenhang mit Search Trees zur Ermittlung der Anzahl möglicherKekulé-Strukturen
Zusammenfassung Das Modell erlaubt mit der im Titel genannten Kombination eine neuartige Methode zur Ermittlung und Generierung vonKekulé-Strukturen. Das Verfahren ist für große benzoide Kohlenwasserstoffe geeignet, die aus cata- und (dünnen) peri-kondensierten Teilstrukturen bestehen.相似文献
156.
The occurrence and magnitude of secondary kinetic isotope effects in the gas phase has been determined for deuterium abstraction from the CD3 group in CD3CH2Cl, CD3CHDCl, and CD3CD2Cl by photochemically generated ground-state chlorine atoms. Over the temperature range 10–94°C a discernible “inverse” kinetic isotope effect is observed. Both the pre-exponential factors and activation energies decrease with deuterium substitution in the vicinal chloromethyl group. The opposing trends result in a net effect close to unity. 相似文献
157.
Detailed spectral simulations based on ab initio density functional theory computations of the amide I and II infrared (IR) and vibrational circular dichroism (VCD) spectra for Ac-(Ala)(4)-NH(2), Ac-(Aib-Ala)(2)-NH(2), and Ac-(Aib)(4)-NH(2) constrained to 3(10)- and alpha-helical conformations are presented. Parameters from these ab initio calculations are transferred onto corresponding larger oligopeptides to simulate the spectra for dodecamers. The differences between conformations and for different Aib substitution patterns within a conformation are reflected in observable spectral patterns where data are available. Simulated IR spectra show small frequency shifts in the amide I maxima between 3(10)- and alpha-helices, but the same magnitude shifts occur within one conformation upon Aib substitution. Thus, from a computational basis, the frequency of the amide I maximum does not discriminate between the 3(10)- or alpha-helical conformations. Calculated VCD band shapes for 3(10)-helices showed more significant changes in amplitude, with change in the fraction of Aib, than those for alpha-helices. Generally, with increasing Aib content, the overall amide I VCD intensity becomes weaker and the amide I couplet becomes more conservative, while the amide II VCD is less affected. Although the detailed band shape is shown to be sensitive to alpha-Me substitution, the basic pattern of amide I and II relative VCD intensities still differs between alpha- and 3(10)-helices and, as a consequence, successfully discriminates between them. These predictions are all borne out in experimental spectra of Aib, mixed Aib-Ala, and Ala-based helical peptides, where available. 相似文献
158.
Amperometric urea biosensor based on urease and electropolymerized toluidine blue dye as a pH-sensitive redox probe 总被引:4,自引:0,他引:4
Vostiar I Tkac J Sturdik E Gemeiner P 《Bioelectrochemistry (Amsterdam, Netherlands)》2002,56(1-2):113-115
The electropolymerized toluidine blue film deposited on the glassy carbon electrode show amperometrically detectable pH sensitivity. This feature of polytoluidine blue (PTOB) film was used for a construction of an amperometric urea biosensor. We have observed a linear shift of the formal redox potential with increasing pH value between 4 and 8 giving the slope of 81 mV(Delta) pH(-1). Polytoluidine blue film has had a significantly increased stability and higher electrochemical activity compared to the adsorbed monomeric dye. The polytoluidine blue urea biosensor has been operating at a working potential of -200 mV vs. SCE. The sensitivity of the biosensor was 980 nA mM(-1) cm(-2). The biosensor showed linearity in concentration range up to 0.8 mM with the detection limit of 0.02 mM (S/N=3). 相似文献
159.
From cyclic linear sweep voltammograms of some Cr(III) complexes it is evident that after electron transfer ligand groups are expelled relatively slowly inDMSO and the tetra coordinated complex is formed. The rate constants could be determined in some cases by the methods of cyclic voltammetry. The following compounds were examined: [Cr(en)3]3+, [Cr(acac)(en)2]2+, [Cr(acac)3]. [Cr(dien)2]3+, [Cr(DMSO)6]3+, [Cr(ur)6]3+. For [Cr(en)3]3+ the energy of activation could be determined as well.The dependence of the velocity of ligand elimination on complex structure is discussed.
Untersuchung von Ligandenaustauschreaktionen einiger Cr(III)-Komplexe mittels cyclischer Voltammetrie
Zusammenfassung Bei der Reduktion einiger der folgenden Cr(III)-Komplexe inDMSO läßt sich auf Grund der Voltammogramme auf eine Ligandenabspaltung und Bildung der vierfach koordinierten Cr(II)-Komplexe schließen: [Cr(en)3]3+, [Cr(acac)(en)2]2+, [Cr(acac)3], [Cr(dien)2]3+, [Cr(DMSO)6]3+, [Cr(ur)6]3+. Für das [Cr(en)3]3+ konnten Geschwindigkeitskonstante und Aktivierungsenergie dieser nachgelagerten Reaktion bestimmt werden.Der Einfluß der Struktur des Komplexes auf die Zerfallsgeschwindigkeit wird diskutiert.相似文献
160.
Richard W.M. Ten Hoedt Gerard van Koten Jan G. Noltes 《Journal of organometallic chemistry》1980,201(1):327-342
Thermal decomposition of configurationally pure 1,2-diarylpropenylcopper compounds Z-Vi2CU4Br2 and Z-Vi2Cu4R2 [Vi (2-Me2NC6H4)CC(Me)-(C6H4Me-4), R 2-Me2NC6H4 or 4-MeC6H4CC] predominantly results in the formation of ViH. In contrast, only dimers (ViVi) were formed on thermolysis of (Z-ViCu2OTf)η which is a further illustration of the influence of the counter anion on the reactivity of organocopper cluster compounds. However, in both cases partial inversion of configuration, giving mixtures of isomers, was observed. The thermolysis of (Z-ViCu2OTf)η is discussed in terms of OTf-enhanced intraaggregate electron-transfer processes. The formation of incipient vinyl cations which are η2-coordinated to the copper cluster can explain the observed isomerization.Also in the hydrolysis reaction of Z-Vi2Cu4Br2 mixtures of isomeric ViH compounds were obtained, the E/Z ratio being dependent on the type of reagent used. Mixtures of isomeric ViX compounds (X Br, Cl, I) were formed in the reaction of Z-Vi2Cu4Br2 with I2 and CuCl2. An explanation for the occurrence of isomerization is presented.Dimers (ViVi) were almost absent in the product mixture resulting from the reaction of Z-Vi2Cu4Br2 with CuCl2. In contrast, ViVi is obtained in about 50% yield from the reaction of ViLi with CuCl2 which is in accord with earlier observations for the reaction of aryllithium compounds with cupric halides.Highly selective E-ViBr formation was observed in the reaction of E-ViLi with AgBr. This reaction probably proceeds via a thermally unstable Z-ViAg2Br intermediate. 相似文献