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991.
992.
Shanmugam Easwaramoorthi Dr. Jae‐Yoon Shin Sung Cho Dr. Pyosang Kim Yasuhide Inokuma Eiji Tsurumaki Atsuhiro Osuka Prof. Dr. Dongho Kim Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(44):12005-12017
Donor–acceptor systems based on subporphyrins with nitro and amino substituents at meta and para positions of the meso‐phenyl groups were synthesized and their photophysical properties have been systematically investigated. These molecules show two types of charge‐transfer interactions, that is, from center to periphery and periphery to center depending on the peripheral substitution, in which the subporphyrin moiety plays a dual role as both donor and acceptor. Based on the solvent‐polarity‐dependent photophysical properties, we have shown that the fluorescence emission of para isomers originates from the solvatochromic, dipolar, symmetry‐broken, and relaxed excited states, whereas the non‐solvatochromic fluorescence of meta isomers is of the octupolar type with false symmetry breaking. The restricted meso‐(4‐aminophenyl) rotation at low temperature prevents the intramolecular charge‐transfer (ICT)‐forming process. The two‐photon absorption (TPA) cross‐section values were determined by photoexcitation at 800 nm in nonpolar toluene and polar acetonitrile solvents to see the effect of ICT on the TPA processes. The large enhancement in the TPA cross‐section value of approximately 3200 GM (1 GM=10?50 cm4 s photon?1) with donor–acceptor substitution has been attributed to the octupolar effect and ICT interactions. A correlation was found between the electron‐donating/‐withdrawing abilities of the peripheral groups and the TPA cross‐section values, that is, p‐aminophenyl>m‐aminophenyl>nitrophenyl. The increased stability of octupolar ICT interactions in highly polar solvents enhances the TPA cross‐section value by a factor of approximately 2 and 4, respectively, for p‐amino‐ and m‐nitrophenyl‐substituted subporphyrins. On the other hand, the stabilization of the symmetry‐broken, dipolar ICT state gives rise to a negligible impact on the TPA processes. 相似文献
993.
Christophe Aronica Dr. Anna Venancio‐Marques Jérôme Chauvin Dr. Vincent Robert Dr. Gilles Lemercier Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(20):5047-5055
Finely tuned optical properties : The optical properties of substituted protected catechol derivatives can be fine‐tuned (see scheme; TBDMS=tert‐butyldimethylsilyloxy). The DFT‐calculated polarisabilities are compared with experimental data.
994.
Weiying Lin Prof. Lingliang Long Bingbing Chen Wen Tan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(10):2305-2309
The first ratiometric fluorescent probe for hypochlorite has been developed through regulation of the electron‐withdrawing ability of the electron acceptor in an intramolecular charge‐transfer (ICT) system by a deoximation reaction (see figure; EWG=electron‐withdrawing group).
995.
Cimetidine reacting with 1,5-dichloroanthraquinone in acetone solution can produce a charge-transfer complex that shows a strong absorption peak at 343 nm. The absorption value at 343 nm increased with cimetidine concentration in the range of 0.01—0.5 μg/mL, with regression coefficient of 0.9995 and detection limit of 0.006 μg/mL. This simple and sensitive method has been successfully applied to determine cimetidine in tablets and capsules, with average recovery of (98.47±0.92)% and (97.07±1.16)%, respectively. Furthermore, the mole ratio of the complex between cimetidine and 1,5-dichloroanthraquinone is 2∶1, and the mechanism of charge-transfer reaction is explored. 相似文献
996.
Development and Validation of Selective Spectrophotometric Methods for the Determination of Pregabalin in Pharmaceutical Preparation 总被引:1,自引:0,他引:1
Three simple, quick and sensitive methods are described for the spectrophotometric determination of pregabalin (Pgb) in pharmaceutical preparations. Among them, the first two methods are based on the reaction of Pgb as n-electron donors with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) as π-acceptors to give highly colored complex species. The colored products were quantitated spectrophotometrically at 494 and 841 nm for DDQ and TCNQ, respectively. Optimization of the different experimental conditions was conducted. Beer’s law was obeyed in the concentration ranges 2.0—30.0 and 1.5—10 µg•mL-1 for DDQ and TCNQ methods, respectively. The third method is based on the interaction of ninhydrin (NN) with primary amine present in the pregabaline. This reaction produces a blue coloured product in N,N-dimethylformamide (DMF) medium, which absorbs maximally at 573 nm. Beer’s law was found in the concentration range 40.0—180.0 μg•mL-1. The methods were applied successfully to the determination of this drug in pharmaceutical dosage forms. 相似文献
997.
The synthesis and absorption/fluorescence properties of two novel intramolecular charge transfer (ICT) compounds of (fluorene-2-yl)-(9-ethylcarbazole-3-yl) ketene and 1-phenyl-3-(fluorenone-2-yl)-5-(9-ethylcarbazole-3-yl)-2-pyrazoline were reported. The primary structure of the target compounds was characterized by IR and 1H NMR. The systems contained a fluorenone or a propenon group as an electron acceptor (A) and an N-ethylcarbazole and a pyrazoline group as electron donors (D). From the emissive properties it was concluded that the electronic coupling between D and A was sufficient to allow charge transfer in these molecules. The ICT maximal emission displayed a large wavelength shift and Stokes shifts increased in response to the increase of the solvent polarity. The highly solvatochromic properties made the two compounds of great interest as new classes of fluorescent probes, electroluminescent and electrofax materials. 相似文献
998.
Charge transport is one of the most important properties in organic materials. Charge transport properties of triphenylene
discogens with a phenylpropionyloxy or 3-phenylpropenoyloxy side chain have been investigated computationally on the basis
of semi-classical Marcus theory. The results show that three triphenylene derivatives have high charge mobility. Title compounds
have much better electronic mobility than the triphenylene. The triphenylenes containing 3-phenylpropenoyloxy have better
hole mobility, but smaller electronic mobility than the triphenylenes with phenylpropionyloxy. For the triphenylene discogens
with a phenylpropionyloxy, the longer the alkloxy chains, the better the positive charge transfer rate, but the smaller the
negative charge transfer rate.
Supported by the National Natural Science Foundation of China (Grant No. 50673069), the Research Foundation of Education Bureau
of Sichuan Province, China (Grant No. 07ZA093), and Scientific Research Foundation of Sichuan Normal University for Innovation
Groups ( Grant No. 025156) 相似文献
999.
HSU Shaw Ling 《中国科学B辑(英文版)》2009,(1)
The metal atom net charge correlation(MANCC) method was developed in prediction of catalyst activity of asymmetric late-transition metal complexes,2-quinoxalinyl-6-iminopyridine Ni(Ⅱ),2-imino-1,10-phenanthroline Co(Ⅱ) and 2-methoxycarbonyl-6-iminopyridine Pd(Ⅱ) complexes,from the net charge of the metal atom for ethylene polymerization.Dreiding force field was modified according to the X-ray diffraction data.We found that the asymmetric structure of the complexes resulted in a charge differ-ence between two... 相似文献
1000.
T.S. Singh andSivaprasad Mitra 《Journal of photochemistry and photobiology. B, Biology》2009,96(3):193-200
The knowledge of the formation of bile acid micellar aggregates is of great importance because of the biological significance of these compounds and their pharmacological applications. The intramolecular charge transfer (ICT) fluorescence property of trans-ethyl-p-(dimethylamino) cinnamate is used to study the micelles formed by aggregation of three most important bile acids, viz. cholic acid, deoxycholic acid and chenodeoxycholic acid by steady state and picosecond time-resolved fluorescence spectroscopy. The ICT fluorescence band intensity was found to increase with concomitant blue shift with the addition of bile acids. The blue shift in ICT fluorescence maxima as well as decrease in nonradiative decay constants in presence of bile acids indicate the passage of the probe towards the micro domains formed from the aggregated bile acids. Binding constant of the probe with micelles as well as critical micelle concentration and average polarity parameter of the micellar environments were obtained from the variation of fluorescence intensity on increasing concentration of bile acids in the medium. 相似文献