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Emil Pop Marcus E. Brewster J. J. Kaminski Nicholas Bodor 《International journal of quantum chemistry》1989,35(2):315-324
9-Amino-1,2,3,4-tetrahydroacridine (THA ), a potent cholinesterase inhibitor, was recently used in the treatment of Alzheimer's disease. On attempting to prepare a dihydropyridine ? pyridinium salt-based redox chemical delivery system (CDS ) to enhance brain delivery of THA , several of the practical synthetic challenges were examined by using a theoretical MO approach. The structures, reactivities and stability of THA , derivatives of THA and a model compound, 4-aminopyridine, a simple dibasic heterocyclic amine, were studied in the framework of the AM -1 approximation. The study included the possible protonated forms of THA and 4-aminopyridine. The calculated heats of formation showed that ring nitrogen protonated forms are more stable for both THA and 4-aminopyridine. The calculated heats of formation showed that ring nitrogen protonated forms are more stable for both THA and 4-aminopyridine, consistent with experimental results. Electron delocalization is responsible for the remarkable stability of these molecules and for the observed lack of reactivity of the amino group, both in the basic and protonated forms. The site of N-alkylation of the 9-nicotinamide derivative of THA (an intermediate in the synthesis of THA -CDS ) is controlled by electronic, thermodynamic, and steric factors. 相似文献
74.
Klaus Rose Vlastimil MatĚjec Milos Hayer Marie PospiŠilovÁ 《Journal of Sol-Gel Science and Technology》1998,13(1-3):729-733
Various types of UV-curable organically modified siloxanes have been synthesized by the sol-gel method with the aim of fabricating chemically sensitive coatings for silica optical fibers. The refractive index of the coating material can be tailored in the range from 1.46 to 1.56 and sensitivity towards CO2 is achieved by incorporation of amino groups. The interaction of the cured layers with CO2 or with hydrocarbons has been studied in immersion experiments. Both the reaction of CO2 with incorporated amino groups and the penetration of hydrocarbons into the layer induce changes of the light absorption coefficient and the refractive index of the coating which are detected by measuring the output light intensity from the fiber. 相似文献
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77.
Y. Marcus 《Journal of solution chemistry》1987,16(9):735-744
The translational entropy loss on the association of two ions to form an ion pair or 11 complex is overcompensated by a rotational entropy gain, an electrostatic entropy gain, and an entropy gain due to solvent release from translational immobilization. The first three effects can be calculated, leaving the fourth as a difference from the experimental entropy change on association. The ratio of the solvent release entropy gain to the entropy change on melting of the solvent indicates the number of solvent molecules released on the association. A similar value is obtained from data for the volume change on association.Presented as a poster at the 10th International Conference on Non-Aqueous Solvents (ICNAS) at Leuven, Belgium, August 1986, and at the 24th International Congress on Coordination Chemistry (ICCC) at Athens, Greece, August 1986. 相似文献
78.
Summary This paper describes a method for theg synthesis of flavone acetates in a sealed capillary tube. The reaction products are separated and purified on a thin-layer plate. The esters are then hydrolyzed on the plate and the parent flavones regenerated. A simple heating device is used which allows for observation of the reaction.
For part IV of this series see Mikrochim. Acta [Wien]1969, 352. 相似文献
Zusammenfassung Beschreibung der Mikrogrammsynthese von Flavonacetaten in einem verschmolzenen Kapillarröhrchen. Die Reaktionsprodukte werden auf einer Dünnschichtplatte getrennt und gereinigt. Dann verseift man die Ester auf der Platte und stellt die freien Flavone dar. Ein einfaches Heizgerät ermöglicht die Beobachtung der Reaktion.
For part IV of this series see Mikrochim. Acta [Wien]1969, 352. 相似文献
79.
A statistical treatment of data for the standard molar Gibbs free energies of transfer of monovalent ions from water to polar solvents has been made in terms of properties of the solvents and the ions. A common multiple regression equation with seven fitting constants, for almost 200 data points, has been found to describe the data in terms of four solvent properties: their electron donor and acceptor abilities, dielectric constant, and cohesive energy density, and three ionic properties: charge, size, and softness. For the ions Na+, K+, Rb+, Cs+, Tl+, (Ph)4As+, Cl?, Br? and N 3 ? the predictions of the equation are within acceptable error limits of the data, and encourage its application to solvents beyond the thirteen used for the data base. For other ions, e.g. H+, Ag+, and the larger anions, further interactions must be taken into account. 相似文献
80.
John R. Van Camp Tish Young Rosemarie F. Hartman Seth D. Rose 《Photochemistry and photobiology》1987,45(3):365-370
Abstract— Photosensitized pyrimidine dimer splitting characterizes the enzymatic process of DNA repair by the DNA photolyases. Possible pathways for the enzymatic reaction include photoinduced electron transfer to or from the dimer. To study the mechanistic photochemistry of splitting by a sensitizer representative of excited state electron donors, a compound in which an indole is covalently linked to a pyrimidine dimer has been synthesized. This compound allowed the quantitative measurement of the quantum efficiency of dimer splitting to be made without uncertainties resulting from lack of extensive preassociation of the unlinked dimer and sensitizer free in solution. Irradiation of the compound with light at wavelengths absorbed only by the indolyl group (approximately 280 nm) resulted in splitting of the attached dimer. The quantum yield of splitting of the linked system dissolved in N2 0-saturated aqueous solution was found to be 0.04 ± 0.01. The fluorescence typical of indoles was almost totally quenched by the attached dimer. A splitting mechanism in which an electron is efficiently transferred intramolecularly from photoexcited indole to ground state dimer has been formulated. The surprisingly low quantum yield of splitting has been attributed to inefficient splitting of the resulting dimer radical anion. Insights gained from this study have important mechanistic implications for the analogous reaction effected by the DNA photolyases. 相似文献