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51.
Darbost U Rager MN Petit S Jabin I Reinaud O 《Journal of the American Chemical Society》2005,127(23):8517-8525
The host-guest properties of calix[6]tren 1 have been evaluated. The receptor is based on a calix[6]arene that is covalently capped at the narrow rim by a tren unit. As a result, the system presents a concave hydrophobic cavity with, at its bottom, a grid-like nitrogenous core. Despite its well-defined cavity and opening to the outside at the large rim, 1 did not behave as a good receptor for neutral molecules in chloroform. However, it exhibited efficient endo-complexation of ammonium guests. By contrast, the per-protonated host, 1.4H(+), behaved as a remarkable receptor for small organic molecules. The complexation is driven by a strong charge-dipole interaction and hydrogen bonds between the polar guest and the tetracationic cap of the calixarene. Finally, coordination of Zn(2+) to the tren core led to the asymmetrization of calixarene cavity and to the strong but selective endo-binding of neutral ligands. This study emphasizes the efficiency of a receptor presenting a concave hydrophobic cavity that is polarized at its bottom. The resulting combination of charge-dipole, hydrogen bonding, CH-pi, and van der Waals interactions highly stabilizes the supramolecular architectures. Also, importantly, the tren cap allows the tuning of the polarization, offering either a basic (1), a highly charged and acidic (1.4H(+)), or a coordination (1.Zn(2+)) site. As a result, the system proved to be highly versatile, tunable, and interconvertible in solution by simple addition of protons, bases, or metal ions. 相似文献
52.
Uniform, well-dispersed silver particles of various morphologies have been prepared by reducing highly acidic silver nitrate solutions with ascorbic acid in the presence of a sodium naphthalene sulfonate-formaldehyde copolymer as dispersing agent. By varying the temperature of the reaction, the free acid content, the addition rate of the reductant, and the aging time, both isometric and anisotropic silver particles could be obtained. It was found that the latter were formed by aggregation of nanosize subunits, which were identified by electron microscopy and X-ray diffractometry. 相似文献
53.
In this brief work we express the cycle index of the molecular point groups as a function of a limited number of initial geometrical parameters. Such parameters are the number
of elements composing the domain D of sites of substitutions in the molecule belonging to the point group G, and the numbers
of sites of D lying on the symmetry elements
for G. 相似文献
54.
The kinetics of the reaction of manganese(III) with oxalic acid (OA) has been studied in H2SO4 solutions. Under the experimental conditions of 6 × 10–3 <>0 < 0.4=" mol=">–3 and [H2SO4]0 0.2 mol dm–3 the observed pseudo-first order rate constant k
obs follows the expression
相似文献
55.
Laura S. Zamorano Francisco Gavilanes Ivan Yu. Sakharov Robert B. van Huystee Valery L. Shnyrov 《Thermochimica Acta》2004,417(1):67-73
Detailed differential scanning calorimetry (DSC), steady-state tryptophan fluorescence and far-UV circular dichroism (CD) studies, together with enzymatic assays, were carried out to monitor the thermal stability of anionic peanut peroxidase (aPrx) at pH 3.0. The spectral parameters were seen to be good complements to the highly sensitive but integral method of DSC. Thus, changes in far-UV CD corresponded to changes in the overall secondary structure of the enzyme, while changes in intrinsic tryptophan fluorescence emission corresponded to changes in the tertiary structure of the enzyme. The results, supported with data concerning changes in enzymatic activity with temperature, show that thermally induced transitions for aPrx are irreversible and strongly dependent upon the scan rate, suggesting that denaturation is under kinetic control. It is shown that the process of aPrx denaturation can be interpreted with sufficient accuracy in terms of the simple kinetic scheme, , where k is a first-order kinetic constant that changes with temperature, as given by the Arrhenius equation; N is the native state, and D is the denatured state. On the basis of this model, the parameters of the Arrhenius equation were calculated. 相似文献
56.
Ivan Gutman Sabina Gojak Boris Furtula Slavko Radenkovi? Andrej Vodopivec 《Monatshefte für Chemie / Chemical Monthly》2006,46(2):1127-1138
Within classes of isomeric benzenoid hydrocarbons various Kekulé- and Clar-structure-based parameters (Kekulé structure count, Clar cover count, Herndon number, Zhang–Zhang polynomial) are all mutually correlated. This explains why both the total π-electron energy (E), the Dewar resonance energy (DRE), and the topological resonance energy (TRE) are well correlated with all these parameters. Nevertheless, there exists an optimal value of the variable of the Zhang–Zhang polynomial for which it yields the best results. This optimal value is negative-valued for E, around zero for TRE, and positive-valued for DRE. A somewhat surprising result is that TRE and DRE considerably differ in their dependence on Kekulé- and Clar-structure-based parameters. 相似文献
57.
A protocol has been established for the transformation of chiral ortho 1-hydroxyethyl propenyl benzenes under both anaerobic and oxidative mercury(II) mediated conditions to produce chiral isochromanes. Further transformations of the former products yielded chiral isochromanquinones, while the latter afforded the corresponding chiral 4-hydroxyisochromanquinones. 相似文献
58.
Second-, third-, and selected fourth-order contributions to the correlation energy were calculated for a series of simple open-shell systems by means of the previously developed double-perturbation theory in the restricted MO formalism. It was found possible to assign some of the diagrams to self-consistency effects and to approximate in this way the E – E energy difference. A comparison is made with a more rigorous approach, in which the UHF ground-state wave function is expressed as a first-order perturbation expansion based on the RHF reference wave function. Distinguishing between “self-consistency” and “correlation” diagrams for open-shell systems in the RHF formulation represents a special case of a more general problem met in any double-perturbation treatment, such as, e.g., treatments of systems in the external field or perturbation expansions with noncanonical orbitals. 相似文献
59.
Klemens Schachl Hailemichael Alemu K. Kalcher Helmut Moderegger Ivan Svancara Karel Vytras 《Analytical and bioanalytical chemistry》1998,362(2):194-200
A carbon thick film electrode modified with an MnO2-film is investigated as an amperometric detector for hydrogen peroxide in flow-injection analysis (FIA). At an operating potential of +0.48 V vs. Ag/AgCl catalytic oxidation of the analyte is exploited for amperometric monitoring. Experimental parameters, such as pH of the carrier, working potential, flow rate and injection volume, are optimized. The amperometric signals are linearly proportional to the concentration of H2O2 in the range from 0.005 to 10 mg/L, showing a detection limit (3σ) of 2.3 μg/L. The method is applied to the determination of H2O2 in rain water and to a simple assay to quantify glucose in human plasma. 相似文献
60.
Ivan Gutman 《Monatshefte für Chemie / Chemical Monthly》2005,136(6):1055-1069
Summary. The fact that cyclic arrangements of double bonds have a dramatic effect on the behavior of conjugated organic molecules is known since the 19th century. The fact that in monocyclic conjugated systems the size of the cycle and the number of -electrons involved is decisive for their stability (aromaticity) or lack of stability (antiaromaticity) is known since the 1930s. In polycyclic -electron systems several cyclic effects are present simultaneously and their separation became possible only recently. A molecular orbital method has been elaborated, by means of which the energy effects of individual cycles in polycyclic -electron systems can be estimated. This method is briefly outlined and illustrated by pertinent examples. An exhaustive bibliography of the topic considered is given. 相似文献
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