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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
54.
Using recently developed theoretical techniques it has been possible to achieve an exact variational solution of the Schrödinger equation within a modest basis set or one-eleltron functions. The full configuration interaction for this system included a total of 256473 1A1 spin-and space-adapted configurations. Comparison with many-body perturbation theory proves to be quite interesting. 相似文献
55.
Vibrational energy transfer has been studied in S18O2, following pumping of the symmetric stretch (ν1) by a Q-switched CO2 laser. Fluorescence from the asymmetric stretch (ν3) is monitored as a function of time following the laser pulse. This fluorescence rises with a rate constant of 74 ± 10 ms?1 torr?1, and then decays with a rate constant of 3.6 ± 0.1 ms?1 torr?1 for the S18O2 itself. The effect of rare gases on the rise and fall rates was also studied. The results agree well with those on S16O2 and are consistent with a double V-V picture in which the excitation is distributed rapidly between the stretches, but is shared with the bend much more slowly. This produces molecules in which the stretches are much “hotter” than the bend, giving rise to possibilities of laser action on the stretch-to-bend transitions and mode-selective vibrational enhancement of chemical reactions. Also, new results have been derived on the kinetics of V-V processes in mixtures. V-V transfer in various isotopic mixtures of SO2 has been studied and the kinetic analysis indicates that S18O2 and S16O2 exhibit the same V-V rates. 相似文献
56.
We report on phototriggered Ru-S --> Ru-O and thermal Ru-O --> Ru-S intramolecular linkage isomerizations in cis- and trans-[Ru(bpy)2(dmso)2]2+. The cis complex features only S-bonded sulfoxides (cis-[S,S]), whereas the trans isomer is characterized by S- and O-bonded dmso ligands. Both cis-[S,S] and trans-[S,O] exhibit photochromism at room temperature in dmso solution and ionic liquid (IL). Rates of reaction in IL were monitored by UV-visible spectroscopy and are similar to those reported in dmso solution (k(O-->S) ranges from approximately 10(-3) to 10(-4) s(-1)). Cyclic voltammetric measurements of cis-[S,S] and trans-[S,O] are consistent with an electrochemically triggered linkage isomerism mechanism. While both cis-[S,S] and trans-[S,O] are photochromic at room temperature, neither complex is emissive. However, upon cooling to 77 K, cis-[S,S] exhibits LMCT (ligand-to-metal charge transfer) emission typical of many ruthenium polypyridine complexes. In contrast to cis-[S,S], trans-[S,O] does not show any detectable emission even at 77 K. 相似文献
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Multivalent cations can cause DNA to condense from its extended state in solution into high-density toroid-shaped particles. Developing methods to control the size and size distribution of DNA toroids is an important goal for the development of artificial gene delivery systems. Here we demonstrate that changes in salt conditions, prior to condensation by multivalent cations, can significantly affect DNA condensation. Specifically, millimolar concentrations of MgCl2 are shown to cause the formation of toroid clusters, whereas NaCl at the same ionic strength does not. 相似文献
59.
The syntheses of two enantiomeric tetracyclic compounds, the thieno[3,2-f][pyrrolo[2,1-c][1,2,4]triazolo[4,3-a][1,4]diazepines 10a and 10b are described. Testing of these enantiomers as inhibitors of platelet activating factor (PAF) revealed good enantiospecificity, meaning that one enantiomer is responsible for the observed biological activity. 相似文献
60.
Xudong?Hu Gui-Bing?Zhao S.?V.?B.?Janardhan Garikipati Kim?Nicholas Stanislaw?F.?Legowski Maciej?RadoszEmail author 《Plasma Chemistry and Plasma Processing》2005,25(4):351-370
Laser-induced fluorescence (LIF) is an effective in-situ probe for NO concentrations below 300 ppm in a non-thermal plasma reactor. A new method has been developed to measure in-situ NO concentration in the reactor discharge region using a long-time—on the order of seconds—averaged fluorescence detection. This method, for quantifying NO concentration in a nonthermal plasma reactor, is simpler than a short-time—on the order of nanoseconds—fluorescence detection. For accurate measurement based on the new method, the LIF intensity must be close to the corona-induced fluorescence (CIF) intensity; the CIF intensity serves as a guide in selecting the LIF intensity. We find that a kinetic model proposed earlier works for two-tube reactors and represents the NO concentration in the middle of the reactor, which verifies the assumption of gas plug flow. 相似文献