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101.
Summary The fluoroescence quenching of 1,4-dimethoxynaphthalene (1) and 1,8-dimethoxynaphthalene (2) by tetraphenylporpyrin (3), 9,10-diphenylanthracene (4), and 3-cyano-4-phenyl-6-(p-tolyl)-pyridin-2-one (5) has been studied in chloroform solution. The quenching occursvia a resonance energy transfer mechanism. The rate constant for the energy transfer (k
ET) of donor2 is slower than that of1 by the same acceptors, indicating that the steric effect dominates the ionization potential effect in all systems. The calculated critical transfer distances (R
0) are 17–72 Å. In contrast, charge transfer is the predominant pathway of electronic deexcitation in the fluorescence quenching of donors1 and2 by 7,7,8,8-tetracyanoquinone-dimethane (6) in chloroform. The roles of temperature and geometrical structure of the donors on the efficiency of fluorescence quenching of1 and2 by acceptor6 have also been studied.
Wechselwirkung des angeregten Singlett-Zustands von 1,4- und 1,8-Dimethoxynaphthalin mit einigen organischen Verbindungen: eine Untersuchung zur Fluoreszenzlöschung
Zusammenfassung Die Löschung der Fluoreszenz von 1,4-Dimethoxynaphthalin (1) und 1,8-Dimethoxynaphthalin (2) durch Tetraphenylporphyrin (3), 9,10-Diphenylanthracen (4) und 3-Cyano-4-phenyl-6-(p-tolyl)-pyridin-2-on (5) in Chloroform wurde untersucht. Die Löschung verläuft über einen Resonanzenergietransfermechanismus. Die Geschwindigkeitskonstante für den Energietransfer (k ET) ist bei gleichem Akzeptor für den Donor2 niedriger als für1. Daraus läßt sich schließen, daß in allen untersuchten Systemen der sterische Effekt über den Effekt des Ionisierungspotentials dominiert. Die berechneten kritischen Transferdistanzen betragen 17–72 Å. Im Gegensatz zu diesen Beobachtungen verläuft der vorherrschende Relaxationsmechanismus bei der Fluoreszenzlöschung von1 und2 durch 7,7,8,8-Tetracyanochinon-dimethan (6) über einencharge-transfer-Prozeß. Die Einflüsse von Temperatur und Geometrie der Verbindungen auf die Effizienz der Fluoreszenzlöschung von1 und2 durch den Akzeptor6 wurden ebenfalls untersucht.相似文献
102.
Iodine-poly(2-vinylpyridine-co-styrene-co-divinylbenzene) charge transfer complexes with antibacterial activity 总被引:1,自引:0,他引:1
Angela Cristina Jandrey Mônica Regina Marques Palermo de Aguiar José Luiz Mazzei 《European Polymer Journal》2007,43(11):4712-4718
In this work, we have developed three different copolymers based on 2-vinylpyridine, styrene and crosslinked with divinylbenzene (10-30 mol%). The copolymers were morphologically and chemically characterized by apparent density, swelling degree, elemental analysis, Fourier transform infrared spectrophotometry and optical microscopy. The formation of iodine complexes with these copolymers was carried out by two different procedures: with solvent, or not. The influence of the copolymers structure on the capacity of anchoring iodine has been investigated. The antibacterial properties of polymeric charge transfer complexes were determined towards 103-107 cells/mL dilutions from the auxotrophic AB1157 Escherichia coli strain. 相似文献
103.
The SINDO1 method is modified to include the calculation of molecular anions. Two versions of modifications are presented which are based on charge dependent orbital exponents. Calculated heats of formation and electron affinities are much improved compared to the standard version with fixed orbital exponents.Dedicated to Professor J. Koutecký on the occasion of his 65th birthday 相似文献
104.
105.
YAN Jing-hui ZHANG Hai-yan LI Zhong-tian CAO Jie SONG Li-hong ZHANG Hui-qiu SHI Chun-shan 《高等学校化学研究》2007,23(4):395-398
Nanocrystals of KMgF3 single-doped and codoped with Ce^3+ or/and Yb^3+ were synthesized separately by the mi-croemulsion method. The X-ray diffraction(XRD) patterns were indexed to show that the KMgF3 crystal system was unchanged. The fluorescent spectra of KMgF3: Ce, Yb polycrystal powders were studied and compared with those of the Ce,Yb doped KMgF3 crystals produced using the high-temperature solid phase method. The diffuse reflection spectra and infrared emission of KMgF3: Ce, Yb were investigated. From the results, the authors could confirm that there were charge transfer processes from Ce^3+ to Yb^3+ in both KMgF3: Ce,Yb nanocrystals and polycrystal powders. 相似文献
106.
Renáta Oriňáková Hans-Dieter Wiemhöfer Jürgen Paulsdorf Veronika Barinková Anna Bednáriková Roger M. Smith 《Journal of Solid State Electrochemistry》2006,10(7):458-464
The electrochemical impedance method was applied during the electrochemical deposition of a binary Ni–Co coating on iron powder in a fluidised bed electrode system. The influence of the suspension density on the charge transfer in the course of the electro-deposition process was studied. At a potential of −900 mV (vs. Ag/AgCl/3 M KCl), when the binary Ni–Co layer was formed, the impedance data were characterised by two semicircles with the semicircle at high frequencies being larger in magnitude. A contribution of the diffusion process to the overall current was observed. The optimal suspension density for the charge transfer in the bed was 10×10−3–15×10−3 (i.e., 4–6 g of iron powder in 50 ml of electrolyte). The most probable mechanism of the charge transfer for the studied concentrations of powder particles is the convective mechanism. The iron particles dispersed in the electrolyte were considered to act as either a depolariser or an additional working electrode depending on the applied electrode potential and on the suspension density. 相似文献
107.
利用质量分析离子动能谱和碰撞诱导解离技采研究了邻、间、对二甲苯分子在电子轰击质谱中产生的双电荷离子[C8H10]2+、[C8H9]2+和单电荷离子[C8H10]+。根据测定的电荷分离反应的释放动能T和由此估算的双电荷离子电荷分离反应过渡态两电荷间距R,推测出过渡态的结构,利用单电荷离子[C8H10]+的MIKES/CID谱可区分邻二甲苯与间、对二甲苯异构体. 相似文献
108.
The growth of ordered domains in lattice gas models, which occurs after the system is quenched from infinite temperature to a state below the critical temperatureT
c, is studied by Monte Carlo simulation. For a square lattice with repulsion between nearest and next-nearest neighbors, which in equilibrium exhibits fourfold degenerate (2×1) superstructures, the time-dependent energy E(t), domain size L(t), and structure functionS(q, t) are obtained, both for Glauber dynamics (no conservation law) and the case with conserved density (Kawasaki dynamics). At late times the energy excess and halfwidth of the structure factor decrease proportional tot
–x, whileL(t) t
x, where the exponent x=1/2 for Glauber dynamics and x1/3 for Kawasaki dynamics. In addition, the structure factor satisfies a scaling lawS(k,t)=t
2xS(ktx). The smaller exponent for the conserved density case is traced back to the excess density contained in the walls between ordered domains which must be redistributed during growth. Quenches toT>T
c, T=Tc (where we estimate dynamic critical exponents) andT=0 are also considered. In the latter case, the system becomes frozen in a glasslike domain pattern far from equilibrium when using Kawasaki dynamics. The generalization of our results to other lattices and structures also is briefly discussed. 相似文献
109.
For real a correspondence is made between the Julia setB
forz(z–)2, in the hyperbolic case, and the set of-chains±(±(±..., with the aid of Cremer's theorem. It is shown how a number of features ofB can be understood in terms of-chains. The structure ofB
is determined by certain equivalence classes of-chains, fixed by orders of visitation of certain real cycles; and the bifurcation history of a given cycle can be conveniently computed via the combinatorics of-chains. The functional equations obeyed by attractive cycles are investigated, and their relation to-chains is given. The first cascade of period-doubling bifurcations is described from the point of view of the associated Julia sets and-chains. Certain Julia sets associated with the Feigenbaum function and some theorems of Lanford are discussed.Supported by NSF grant No. MCS-8104862.Supported by NSF grant No. MCS-8203325. 相似文献
110.
The bifurcations of periodic orbits in a class of autonomous three-variable, nonlinear-differential-equation systems possessing a homoclinic orbit associated with a saddle focus with eigenvalues ( ±i,), where ¦/¦ < 1 (Sil'nikov's condition), are studied in a two-parameter space. The perturbed homoclinic systems undergo a countable set of tangent bifurcations followed by period-doubling bifurcations leading to periodic orbits which may be attractors if ¦/¦ < 1/2. The accumulation rate of the critical parameter values at the homoclinic system is exp(-2¦/¦). A global mechanism for the onset of homoclinicity in strongly contractive flows is analyzed. Cusp bifurcations with bistability and hysteresis phenomena exist locally near the onset of homoclinicity. A countable set of these cusp bifurcations with scaling properties related to the eigenvalues±i of the stationary state are shown to occur in infinitely contractive flows. In the two-parameter space, the periodic orbit attractor domain exhibits a spiral structure globally, around the set of homoclinic systems, in which all the different periodic orbits are continuously connected. 相似文献