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151.
Zhen-Yu Yang 《Journal of fluorine chemistry》2004,125(5):763-765
Substituted phenyl iodides or diiodides reacted with ethyl iodotetrafluoroproponylate ICF2CF2CO2Et, 1 in the presence of copper powder to give the coupled products 2 or 3 in good yields. Addition of 1 to ethylene and allyl acetate proceeded smoothly under thermal and radical conditions to give the corresponding adducts, which underwent elimination reaction to give β-vinyl and β-allyl α,α,β,β-tetrafluoroesters, CH2CHCF2CF2CO2Et, 4 and CH2CHCH2CF2CF2CO2Et, 5, respectively. 1 also readily reacted with 1,5-hexadiene and 1-hexene with copper or palladium complex, followed by reduction to remove iodine to produce ω-alkenyl-α,α,β,β-tetrafluoroester CH2CH(CH2)4CF2CF2CO2Et 6 and α,α,β,β-tetrafluoroester C4H9CH2CHICF2CF2CO2Et. 相似文献
152.
153.
154.
ZHANG Jing HUANG Ru-dan ZHU Oin-lei HU Chang-wen 《高等学校化学研究》2007,23(4):483-485
Introduction In recent years,considerable attention has been paid to supramolecular networks based on metal organic building blocks because of their potential applications in diverse fields,such as,catalysis,optics,sensors, magnetism,and molecular recognition[1-3].On the ba- 相似文献
155.
156.
Sébastien Fiorucci Jer?me Golebiowski Daniel Cabrol-Bass Serge Antonczak 《Chemphyschem》2004,5(11):1726-1733
Flavonoids are naturally occurring phenol derivatives present in substantial amounts in a large variety of plants, fruits and vegetables daily eaten by humans. Most of these compounds exhibit several interesting biological activities, such as antiradical and antioxidant actions. Indeed, by complexation with specific enzymes, flavonoids are notably liable to metabolize molecular dioxygen. On the basis of experimental results describing oxygenolysis of the flavonoid quercetin, activated by the enzyme quercetin 2,3-dioxygenase (2,3-QD),ur attention has focused on the role of metal center in the activation of the substrate quercetin. Thus, in the present study, by means of DFT calculations at the B3LYP/ 6-31(+)G* level on model molecular systems, we describe different mechanisms for dioxygen metabolization by quercetin. Stationary points are described, and energetic and structural analyses along the reaction paths are reported. Our calculations show that the copper cation must act as an oxidant towards the substrate and that the reaction proceeds through a 1,3-cycloaddition. 相似文献
157.
158.
Interatomic distances in the transition state were estimated for the reactions of radical abstraction: H· + H2, H· + HCl, H· + CH4, N·H2 + NH3, HO· + H2O, HO2
· + HOOH, and C·H3 + SiH4. The calculation was performed by the quantum-chemical density functional method or coupled clusters method (QCH), as well as by the methods of intersecting parabolas (IPM) and Morse curves (IMM), using experimental data (activation energies and reaction enthalpies). The results of the latter two methods are close to the quantum-chemical calculation and differ only by the increment a: r(IPM or IMM) = a + r(QCH), where a = –4.5·10–12 m for IPM and a = +1.9·10–12 m for IMM. 相似文献
159.
The mechanism of the indium electrodeposition on gold from acidic KBr solutions has been investigated by means of the rotating ring-disc electrode technique. The measurements showed that the overall electrode reaction In(III) + 3 e In consists of two successive charge transfer steps, i.e. In(III) + 2 e In(I) and In(I) + e In, with soluble monovalent indium as an intermediate. The current efficiency for In(I) generation under steady-state conditions is 100% in the case of low disc current densities. The disproportionation of In(I) in the bulk of solution occurs in slightly acidified solutions,pH=2, in addition to the In(I) electrochemical reduction. Based on the ring current transients, it was established that the two-electron transfer step is preceded by the formation of a thin passive film of indium metal.
Untersuchung der elektrochemischen Reduktion von In(III)-Ionen an Gold in sauren Bromidlösungen mit der rotierenden Ring-Scheiben-Elektrode
Zusammenfassung Mit Hilfe der rotierenden Ring-Scheiben-Elektrode wurde der Mechanismus der kathodischen Abscheidung von Indium auf Gold in sauren KBr-Lösungen untersucht. Aus den Messungen folgt, daß die Bruttoreaktion In(III) + 3e In über zwei aufeinanderfolgende Durchtrittsreaktionen, In(III) + 2 e In(I) und In(I) + e In, mit löslichem einwertigem Indium als Zwischenprodukt abläuft. Bei kleinen Stromdichten werden die In(I)-Ionen mit 100%iger Stromausbeute erzeugt. In schwächer sauren Lösungen (pH=2) konnte außer der elektrochemischen Reduktion von In(I) zusätzlich dessen Disproportionierung innerhalb der Lösung ermittelt werden. Auf Grund der Ringstrom-Zeit-Kurven wurde auch festgestellt, daß die Bildung von einer dünnen In-Metallschicht, die ein passives Verhalten aufweist, dem Zweielektronenübergang vorangegangen ist.相似文献
160.
Delayed feedbacks are quite common in many physical and biological systems and in particular many physiological systems. Delay
can cause a stable system to become unstable and vice versa. One of the well-studied non-biological chemical oscillators is
the Belousov-Zhabotinskii (BZ) reaction. This gives relaxation oscillations for a considerable period of time under batch
conditions. This paper deals with the effect of perturbing the limit cycle oscillation of BZ reaction by employing a delayed
electrical feedback to the system under batch conditions. The parameters chosen to study are external resistance and delay.
For various resistances and delays the system was electrically perturbed and found to exhibit various complex mixed mode oscillations.
The dynamic features are accounted for by the Oregonator model, with time delay incorporated in one of the variables.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献