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Zusammenfassung Anhand der Methode der Konfigurationenwechselwirkung wurde die Ladungsdichteverteilung in einer Reihe von aromatischen Aminen und N-haltigen Heteroaromaten im angeregten Singulett- und Triplettzustand untersucht. Durch die Untersuchungen wurde die Formulierung der folgenden Regel ermöglicht: im angeregten Singulett- und Triplettzustand ist die Basizität bei den Aminen wesentlich vermindert; die N-haltigen Heteroaromaten weisen im angeregten Singulettzustand eine erhöhte Basizität auf, und im Triplettzustand tritt eine Verminderung der Basizität ein.
The electron density distribution in excited singlet and triplet states of a number of aromatic amines and heterocyclic compounds containing nitrogen atoms is studied using the CI-method. The investigation allows the formulation of the following rule: in excited singlet and triplet states the amines possess significantly reduced basicity; the nitrogen heterocyclic compounds in excited singlet states increase their basicity, whereas in excited triplet states their basicity is decreased.
Résumé Au moyen de la méthode d'interaction de configuration, on a étudié la répartition de la densité électronique dans un certain nombre d'aminés aromatiques et de composés hétérocycliques azotés dans l'état excité singulet et triplet.Les études effectuées ont permis d'établir la règle suivante: à l'état excité singulet ou triplet la basicité des aminés est sensiblement réduite; la basicité des composés N-hétérocycliques augmente dans l'état excité singulet et diminue dans le triplet.相似文献
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Petkov N Hölzl M Metzger TH Mintova S Bein T 《The journal of physical chemistry. B》2005,109(10):4485-4491
A new synthesis method for preparation of thin films and powders consisting of zeolite beta nanocrystals embedded in ordered mesoporous silica matrix is described. The final structures possessing bimodal porosity, i.e., high degree of mesophase order and spatially defined microporous zeolite nanocrystals are obtained via simultaneous solvent evaporation of preformed silica/surfactant/ethanol/nanosized zeolite beta assemblies. The films were characterized with grazing-incident diffraction (GID), nitrogen sorption based on gravimetric measurements with quartz crystal microbalance (QCM) devices, and transmission electron microscopy (TEM). It is shown that the incorporation of beta nanocrystals in the mesoporous silica matrix and the mesophase order itself can be controlled through the variation of the fractional amounts of the zeolite nanoparticles and silica/surfactant solutions. The HR-TEM measurements showed that the nanosized Beta microporous crystals are separated and at the same time connected through an ordered mesostructured matrix. 相似文献
5.
A new procedure for the preparation of high aspect ratio Au nanowires utilizing gold electroless reduction in the hexagonally ordered, thiol-modified nanosized channels of the SBA-15 material is reported. Two different Au precursors were adsorbed onto pedant thiol groups, covalently bonded to the mesoporous silica surface, and used as seeds to grow extended Au nanostructures by treatment in Au electroless reduction bath. It is shown that the dimensions and the assembly of the Au seeds are important parameters for the subsequent electroless reduction process. The [AuCl4]- ions complexed to the TOAB molecules assembled on the thiol-modified mesoporous surface of the SBA-15 material are suitable precursors for the subsequent gold electroless reduction. The resulting structures are several micrometer long Au nanowires with uniform diameters of about 5 nm, having large single-crystalline domains. The TEM results clearly show that the growth of the Au nanowires is templated by the channel structure of the SBA-15 material. 相似文献
6.
Micellization and interfacial properties of alkyloxyethylene sulfate surfactants in the presence of multivalent counterions 总被引:1,自引:0,他引:1
Alkyloxyethylene sulfates are a special class of surfactants that are unusually stable in the presence of multivalent counterions and are not as prone to precipitation as anionic surfactants without intermediate ethoxy groups in the molecule. However, formation of micelles, their structure, and the properties of monolayers of these surfactants exhibit very interesting and sometimes unexpected properties depending on the nature of the ions dissolved in the solution. This paper presents a brief overview of our recent efforts to reveal the nature of these properties, including some new results. We show that the strong binding of multivalent (and particularly trivalent counterions) triggers a sphere-to-cylinder shape transition of the micelles and facilitates their further growth, even at very low ionic strength. The properties of surfactant monolayers are coupled to those of the micelles in the bulk and are governed also by multivalent counterion binding. The effect of multivalent counterions on the aggregation and structure formation in anionic surfactant solutions has both fundamental and practical importance. 相似文献
7.
Using kinetic isotope effects (KIE) and Hammett correlations, we show that the main role of the adenosine 2′-OH group on deprotonation by the non nucleophilic base DBU during external acyl group transfer is to generate enhanced electron density on the attacking nucleophile through ionization. The small primary KIEs (1.2 and 1.6) and the large Hammett reaction constants (+2.25 and +3.19) obtained for the ethanolysis of 2′/3′-O-p-substituted benzoyl 5′-O-trityl adenosines and 2′-deoxyadenosines are consistent with an AN + DN reaction mechanism. The implications of our results are discussed in terms of chemical contributions of the 2′-OH group in the ribosome catalysis of peptide bond formation. 相似文献
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D. Kocheva G. Rainovski J. Jolie N. Pietralla A. Blazhev A. Astier R. Altenkirch S. Ansari Th. Braunroth M. L. Cortés A. Dewald F. Diel M. Djongolov C. Fransen K. Gladnishki A. Hennig V. Karayonchev J. M. Keatings E. Kluge J. Litzinger C. Müller-Gatermann P. Petkov M. Rudigier M. Scheck Ph. Scholz P. Spagnoletti M. Spieker C. Stahl R. Stegmann M. Stoyanova P. Thöle N. Warr V. Werner W. Witt D. Wölk K. O. Zell P. Van Isacker V. Yu. Ponomarev 《The European Physical Journal A - Hadrons and Nuclei》2017,53(9):175
9.
Abdullahi Garba USMAN Selin IIK Sani Isah ABBA Filiz MERL 《Turkish Journal of Chemistry》2020,44(5):1339
Isoquercitrin is a flavonoid chemical compound that can be extracted from different plant species such as Mangifera indica (mango), Rheum nobile , Annona squamosal , Camellia sinensis (tea), and coriander ( Coriandrum sativum L.). It possesses various biological activities such as the prevention of thromboembolism and has anticancer, antiinflammatory, and antifatigue activities. Therefore, there is a critical need to elucidate and predict the qualitative and quantitative properties of this phytochemical compound using the high performance liquid chromatography (HPLC) technique. In this paper, three different nonlinear models including artificial neural network (ANN), adaptive neuro-fuzzy inference system (ANFIS), and support vector machine (SVM),in addition to a classical linear model [multilinear regression analysis (MLR)], were used for the prediction of the retention time (tR) and peak area (PA) for isoquercitrin using HPLC. The simulation uses concentration of the standard, composition of the mobile phases (MP-A and MP-B), and pH as the corresponding input variables. The performance efficiency of the models was evaluated using relative mean square error (RMSE), mean square error (MSE), determination coefficient (DC), and correlation coefficient (CC). The obtained results demonstrated that all four models are capable of predicting the qualitative and quantitative properties of the bioactive compound. A predictive comparison of the models showed that M3 had the highest prediction accuracy among the three models. Further evaluation of the results showed that ANFIS–M3 outperformed the other models and serves as the best model for the prediction of PA. On the other hand, ANN–M3proved its merit and emerged as the best model for tR simulation. The overall predictive accuracy of the best models showed them to be reliable tools for both qualitative and quantitative determination. 相似文献
10.
V. B. Petkov E. V. Bugaev P. A. Klimai M. V. Andreev V. I. Volchenko G. V. Volchenko I. M. Dzaparova D. D. Dzhappuev A. N. Gaponenko Zh. Sh. Guliev N. F. Klimenko A. U. Kudzhaev A. V. Sergeev N. S. Khaerdinov A. B. Chernyaev A. F. Yanin 《Journal of Experimental and Theoretical Physics》2010,110(3):406-416
The energy spectra and temporal characteristics of high-energy gamma-ray bursts from evaporating primordial black holes have been calculated using various evaporation models. The currently existing theoretical uncertainties in the shape of the evaporated photon spectrum are discussed. The data from the Andyrchy and Carpet-2 arrays of the Baksan Neutrino Observatory (Institute for Nuclear Research, Russian Academy of Sciences) obtained in the mode of detection of a single cosmic-ray component are used to search for cosmic gamma-ray bursts with a primary photon energy of about 8 GeV. New upper limits have been obtained for the number density of evaporating black holes in a local region of space with a characteristic size of ~10?3 pc for various evaporation models. 相似文献