The surface chemistry of oxides is relevant for many technological applications: catalysis, photoelectrolysis, electronic-device
fabrication, prevention of corrosion, sensor development, etc. This article reviews recent theoretical works that deal with
the surface chemistry of oxides. The account begins with a discussion of results for the adsorption of CO and NO on oxides,
systems which have been extensively studied in the literature and constitute an ideal benchmark for testing the quality of
different levels of theory. Then, systematic studies concerned with the behavior of adsorbied alkali metals and sulfur-containing
molecules are presented. Finally, a correlation between the electronic and chemical properties of mixed-metal oxides is analyzed
and basic principles for designing chemically active oxides are introduced. Advances in theoretical methods and computer capabilities
have made possible a fundamental understanding of many phenomena associated with the chemistry of molecules on oxide surfaces.
Still many problems in this area remain as a challenge, and the approximate nature of most theoretical methods makes necessary
a close coupling between theory and experiment. Following this multidisciplinary approach, the importance of band-orbital
interactions for the reactivity of oxide surfaces has become clear. Simple models based on band-orbital mixing can explain
trends found for the interaction of many adsorbates with oxide surfaces. These simple models provide a conceptual framework
for modifying or controlling the chemical activity of pure oxides and for engineering mixed-metal oxides. In this respect,
theoretical calculations can be very useful for predicting the best ways for enhancing the reactivity of oxide systems and
reducing the waste of time, energy and materials characteristic of an empirical design.
Received: 21 June 2001 / Accepted: 8 October 2001 / Published online: 1 February 2002 相似文献
The title amines were pyrolyzed in a stirred-flow reactor at 380–510°C, pressures of 8–15 torr and residence times of 0.3–2.4 s, using toluene as carrier gas. The substrates with an allyl group yielded propene and iminonitriles as reaction products. HCN is formed by decomposition of the iminonitriles. The first-order rate coefficients for propene formation fit the Arrhenius equations
A series of Bcl-x(L)/Bak antagonists, based on a terephthalamide scaffold, was designed to mimic the alpha-helical region of the Bak peptide. These molecules showed favorable in vitro activities in disrupting the Bcl-x(L)/Bak BH3 domain complex (terephthalamides 9 and 26, K(i) = 0.78 +/- 0.07 and 1.85 +/- 0.32 microM, respectively). Extensive structure-affinity studies demonstrated a correlation between the ability of terephthalamide derivatives to disrupt Bcl-x(L)/Bak complex formation and the size of variable side chains on these molecules. Treatment of human HEK293 cells with the terephthalamide derivative 26 resulted in disruption of the Bcl-x(L)/Bax interaction in whole cells with an IC(50) of 35.0 microM. Computational docking simulations and NMR experiments suggested that the binding cleft for the BH3 domain of the Bak peptide on the surface of Bcl-x(L) is the target area for these synthetic inhibitors. 相似文献
The electroreductions of the NAD+ model compounds nicotinamide (I), N1-methyl nicotinamide (II), N′-methyl nicotinamide (III) and isonicotinamide (IV) on carbon electrodes have been studied in aqueous media in the pH range 0–12 by linear-sweep cyclic voltammetry (Scheme 1, I-IV). Logarithmic analyses of the reduction peaks were performed by computing the convolution of the current with time as a function of the potential. On the basis of the experimental results it was concluded that the irreversibility of the electron transfers increased when a glassy carbon electrode was used, and this irreversibility being more marked when a plastic formed carbon electrode was employed. The reduction processes occurred with more difficulty on carbon electrodes than on mercury electrodes. Both the reduction and the reoxidation (when occurred) processes changed with respect to those observed on mercury electrodes, being irreversible electron transfers the rate-determining steps in most cases. Thus, for compounds I, II and III at pH < 2 the reductions occurred by the uptake of two electrons and two H+ ions, and the rate determining step was found to be the first one-electron transfer, for I and III, and the irreversible second electron transfer, preceded by the uptake of an H+ ion, for II. At pH>3 the processes consisted of electrodimerization reactions, preceded by the protonation of the heterocyclic nitrogen in cases I and III. The second electron transfer of the electroreduction of IV always appeared irreversible, in contrast with that found for mercury electrodes. 相似文献
Reaction of N-(4-pyridylmethyl)benzamide N-oxides with acetic anhydride yielded dimerization compounds. This dimerization occurs at the atom attached to the pyridine ring. These compounds so obtained were evaluated for analgesic and antiinflammatory activity. 相似文献
Evolution algebras are a special class of nonassociative algebras exhibiting connections
with various fields of mathematics.
Hilbert evolution algebras generalize the concept in the framework of Hilbert spaces.
This allows us to deal with a wide class of infinite-dimensional spaces.
We study Hilbert evolution algebras associated to a graph.
Inspired by the definitions of evolution algebras we define the Hilbert evolution algebra
that is associated to a given graph and the Hilbert evolution algebra that is associated
to the symmetric random walk on a graph.
For a given graph, we provide the conditions for these structures to be or not to be isomorphic.
Our definitions and results extend to the graphs with infinitely many vertices.
We also develop a similar theory for the evolution algebras associated to finite graphs.
We establish Bernstein-type inequalities for rational functionswith prescribed poles in the Chebyshev norm on the unit circlein the complex plane. Generalizations of polynomial inequalitiesof Erds-Lax and Turán are also obtained for such rational functions with restricted zeros. 相似文献