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1.
Normal and second excimers in macromolecules—I: Poly(1-methoxy-4-vinylnaphthalene) in fluid solution
The emission properties of poly(1-methoxy-4-vinylnaphthalene) (PMVN) in 2-methyltetrahydrofuran solution have been investigated over the range 77–350 K. It exhibits, in addition to the monomer fluorescence (348 and 360 nm), two structureless emissions derived from two different types of excimer, viz. the normal excimer (420 nm) and the second excimer (380 nm), the latter having a partially overlapping structure of aromatic rings. The intensity of second excimer emission of PMVN increases with decreasing temperature, while the normal excimer emission shows a maximum at 215 K. Kinetic analysis of transient decay curves for the fluorescence of PMVN gave results consistent with the previously reported kinetic scheme for the dimer model, 1,3-bis(4-methoxy-1-naphthyl)propane, showing that the second excimer is not formed from or converted to the normal excimer and that two types of excimer are formed independently from the excited monomer. 相似文献
2.
In this paper, the interaction between herbacetin and BSA was investigated by fluorescence and three-dimensional fluorescence spectroscopy under simulated physiological conditions. It was proved that the fluorescence quenching of BSA by herbacetin was mainly the result of the formation of a herbacetin–BSA complex. The modified Stern–Volmer quenching constant and the corresponding thermodynamic parameters ΔH 0, ΔG 0 and ΔS 0 were calculated at different temperatures. The results indicated that electrostatic interactions were the predominant intermolecular forces in stabilizing the complex. The distance r=3.23 nm between the donor (BSA) and acceptor (herbacetin) was obtained according to Förster’s nonradioactive energy transfer theory. The synchronous fluorescence and three-dimensional fluorescence spectra results showed that the hydrophobity of amino acid residues increased in the presence of herbacetin. These results revealed that the microenvironment and conformation of BSA changed during the binding reaction. 相似文献
3.
G. Pistolis & Angelos Malliaris 《Supramolecular chemistry》2013,25(6):395-402
The complexation of the bifluorophore 1,3-bis(pyrenyl)propane with γ-cyclodextrin in water has been studied by means of steady state and time-resolved fluorescence spectroscopy. It was found that in the association with γ-cyclodextrin the propane chain of 1,3-bis(pyrenyl)propane folds and the two pyrene units enter the same cyclodextrin cavity where they form weakly bound ground state dimers, which upon excitation emit excimer fluorescence. In addition to this 1:1 excimer emitting complex, two more complexes were detected, which emit monomer pyrene fluorescence. One has 1:1 stoichiometry, i.e. isomeric to the previous complex, and the other, with 2:1 stoichiometry, is comprised of two γ-cyclodextrin units and one 1,3-bis(pyrenyl)propane. 相似文献
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5.
Wanju Zhang Xujie Xiong Fang Wang Yushu Ge Yi Liu 《Journal of solution chemistry》2013,42(6):1194-1206
Ronidazole (RNZ) is widely used for the therapeutic treatment of farmed animals and is suspected of being a human carcinogen and mutagen. The interaction between RNZ and human serum albumin (HSA) was investigated systematically by fluorescence spectroscopy, synchronous fluorescence, three-dimensional fluorescence, CD spectroscopy, UV–vis absorption spectroscopy and a molecular docking study. The results indicate that the probable quenching mechanism of HSA by RNZ is dynamic quenching. The corresponding thermodynamic parameters, such as ΔH, ΔS and ΔG, etc., were calculated according to the van’t Hoff equation. The results indicate that the forces acting between RNZ and HSA are mainly hydrogen bonds and van der Waals forces. The conformational changes in the interaction were studied by synchronous fluorescence, CD spectroscopy and three-dimensional fluorescence spectra. The results reveal that the microenvironment and conformation of HSA has been changed. A molecular modeling study further confirmed the binding mode obtained by the experimental studies. 相似文献
6.
Yongnian Ni Shaojing Su Serge Kokot 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2010,75(2):547-552
The interaction between fluoroquinolones (FQs), ofloxacin and enrofloxacin, and bovine serum albumin (BSA) was investigated by fluorescence and UV–vis spectroscopy. It was demonstrated that the fluorescence quenching of BSA by FQ is a result of the formation of the FQ–BSA complex stabilized, in the main, by hydrogen bonds and van der Waals forces. The Stern–Volmer quenching constant, KSV, and the corresponding thermodynamic parameters, ΔH, ΔS and ΔG, were estimated. The distance, r, between the donor, BSA, and the acceptor, FQ, was estimated from fluorescence resonance energy transfer (FRET). The effect of FQ on the conformation of BSA was analyzed with the aid of UV–vis absorbance spectra and synchronous fluorescence spectroscopy. Spectral analysis showed that the two FQs affected the conformation of the BSA but in a different manner. Thus, with ofloxacin, the polarity around the tryptophan residues decreased and the hydrophobicity increased, while for enrofloxacin, the opposite effect was observed. 相似文献
7.
Yunyou Zhou Huapeng Yu Li Zhang Junyong Sun Lian Wu Qin Lu Lun Wang 《Journal of inclusion phenomena and macrocyclic chemistry》2008,61(3-4):259-264
The inclusion behavior of cucurbit [7] uril with acridine orange was investigated by fluorescence spectrometry in acetate buffer solution. It was found that the fluorescence intensity of acridine orange regularly increased upon the addition of cucurbit [7] uril accompanying with blue-shift of the position of the emission maximum. The results indicate the formation of the complex at a 1:1 complex stoichiometry and the association constant was calculated by applying a deduced equation. From the temperature dependence of the equilibrium constants, ΔH and ΔS values were obtained, indicating an enthalpic driving force for complexation. Meanwhile, the possible interaction mechanism was also discussed. 相似文献
8.
《Journal of Photochemistry》1985,28(2):237-253
The fluorescence decays of 1,3-di(1-pyrenyl)propane undergoing intramolecular excimer formation can be fitted to a sum of three exponentials, whereas only two exponentials are needed for 1,3-di(2-pyrenyl)propane. It is concluded, from an analysis of the decay parameters, that one monomer and two excimers are involved in the excimer formation for 1,3-di(1-pyrenyl)-propane, in contrast with that for 1,3-di(2-pyrenyl)propane where only one excimer and one monomer are needed in the kinetic scheme. Kinetic and thermodynamic data are presented for both molecules. The significance of the various cases (double and higher) of multi-exponential decay is discussed. 相似文献
9.
Poly(4-vinylbiphenyl) and copolymers of methyl methacrylate and 4-vinylbiphenyl show both monomeric (λmax = 325 nm) and excimer (λmax = 380 nm) fluorescence. The quantum yield of excimer emission increases and the monomeric emission decreases with increase in the fraction of vinylbiphenyl units in the copolymer. The decrease of the monomeric emission is closely related to a decrease in singlet lifetime. These results are interpreted in terms of a kinetic controlled excimer formation. Comparison of the emission in the homo and copolymers with that of the dimeric model compound shows that excimer formation in the polymer strongly depends upon the possibility of energy migration along sequences of vinylbiphenyl units. This conclusion is considered as of particular relevance due to the change in geometry of the biphenyl unit upon excitation. 相似文献
10.
Nitroxoline is a wide spectrum antibacterial and is one of the most important urinary antiseptics.The interaction between nitroxoline and human serum albumin(HSA)has been investigated systematically by fluorescence spectroscopy,synchronous fluorescence,three-dimensional fluorescence,CD spectroscopy and UV-Vis absorption spectroscopy.The results indicated that the quenching of HSA by nitroxoline was static.The corresponding thermodynamic parameters △H,△S and △G calculated according to van’t Hoff equation revealed that the intermolecular forces acting between nitroxoline and HSA were mainly hydrogen bonding and van der Waals forces.The conformational changes in the interaction were studied by synchronous fluorescence,CD spectroscopy and three-dimensional fluorescence spectra which showed changes in the microenvironment and conformation of HSA. 相似文献
11.
The interaction between glyoxal-bis-(2-hydroxyanil) (GBH) and bovine serum albumin (BSA) was studied by spectroscopic methods including fluorescence spectroscopy, circular dichroism (CD) and UV–visible absorption spectra. The mechanism for quenching the fluorescence of BSA by GBH is discussed. The number of binding sites n and observed binding constant K b were measured by the fluorescence quenching method. The thermodynamic parameters ΔH θ , ΔG θ , and ΔS θ were calculated at different temperatures and the results indicate that hydrogen bonding and van der Waals forces played major roles in the reaction. The distance r between the donor (BSA) and acceptor (GBH) molecules was obtained according to Förster’s theory of non-radiation energy transfer. Synchronous fluorescence and three-dimensional fluorescence spectra were used to investigate the structural change of BSA molecules that occur upon addition of GBH, and these results indicate that the secondary structure of BSA molecules is changed by the presence of GBH. 相似文献
12.
The binding of caffeine to human serum albumin (HSA) under physiological conditions has been studied by the methods of fluorescence, UV-vis absorbance and circular dichroism (CD) spectroscopy. The mechanism of quenching of HSA fluorescence by caffeine was shown to involve a dynamic quenching procedure. The number of binding sites n and apparent binding constant K b were measured by the fluorescence quenching method and the thermodynamic parameters ΔH, ΔG, ΔS were calculated. The results indicate that the binding is mainly enthalpy-driven, with van der Waals interactions and hydrogen bonding playing major roles in the reaction. The distance r between donor (HSA) and acceptor (caffeine) was obtained according to the Förster theory of non-radiative energy transfer. Synchronous fluorescence, CD and three-dimensional fluorescence spectroscopy showed that the microenvironment and conformation of HSA were altered during the reaction. 相似文献
13.
The binding of isothipendyl hydrochloride (IPH) to bovine serum albumin (BSA) was investigated by fluorescence spectroscopy combined with UV-visible absorption and circular dichroism (CD) techniques under simulative physiological conditions for the first time. The quenching mechanism of fluorescence BSA by IPH was discussed. The binding parameters have been evaluated by fluorescence quenching method. The thermodynamic parameters, ΔH°, ΔS° and ΔG° calculated at different temperatures indicated that the hydrophobic force played a major role in the interaction of IPH to BSA. The distance, r between donor (BSA) and acceptor (IPH) was obtained according to the Förster's theory of non-radiation energy transfer and was found to be 2.21 nm. Experimental results showed that the α-helicity of BSA decreased from 66.4% (in free BSA) to 39.1% (in bound BSA). The effect of common ions on the binding constant was also investigated. 相似文献
14.
《Tetrahedron: Asymmetry》1999,10(23):4463-4467
Water-soluble palladium complexes with sulfonated diphosphines dpppts (1,3-bis[di(m-sodiumsulfonatophenyl)phosphino]propane), dppbts (1,4-bis[di(m-sodiumsulfonatophenyl) phosphino]butane), (S,S)-BDPPTS (2,4-bis[di(m-sodiumsulfonatophenyl)phosphino]butane) and (R,R)-CBDTS (1,2-bis[di(m-sodiumsulfonatophenyl)phosphinomethyl]cyclobutane) are active in the hydrocarboxylation of vinyl arenes without addition of acid. The stability of the catalyst systems increases when the reaction is performed in an acidic medium and the catalysts could be recycled twice with no loss in activity or enantioselectivity in the case of the [Pd(OAc)2]/BDPPTS system. Enantioselectivities up to 43% are obtained. 相似文献
15.
The interactions between fluoroquinolones and human serum albumin (HSA) were investigated by affinity capillary electrophoresis (ACE) and fluorescence quenching technique. Based on the efficient separation of several fluoroquinolones using a simple phosphate buffer, the binding constants of fluoroquinolones with HSA were determined simultaneously during one set of electrophoresis by ACE method. The thermodynamic parameters were obtained from data at different temperatures, and the negative ΔH and ΔS values showed that both hydrogen bonds and van der Waals interaction played major roles in the binding of fluoroquinolones to HSA. The interactions were also studied by fluorescence quenching technique. The results of fluorescence titration revealed that fluoroquinolones had the strong ability to quenching the intrinsic fluorescence of HSA through the static quenching procedure. The binding site number n, apparent binding constant Kb and the Stern-Volmer quenching constant Ksv were determined. The thermodynamic parameters were also studied by fluorescence method, and the results were consonant with that of ACE. 相似文献
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17.
The kinetics of excimer formation and decay in dilute dichloromethane solutions of poly(N-vinyl carbazole) have been investigated using time-resolved fluorescence spectroscopy. Further evidence for dual excimer formation in this polymer is presented; interconversion of the excimeric states appears to be a significant process at room temperature. 相似文献
18.
The applicability of the PPP-method for the calculation of fluorescence bands and intensities is tested on a series of substituted coumarines. The calculated wavenumbers of the fluorescence transitions are in excellent agreement with the experimental data whereas the theoretical oscillator strengths of the S1 → S0 transition or the differences, ΔA, of the Julg-indices in the first excited state and the ground state yield only poor correlations with the measured fluorescence intensities. 相似文献
19.
The dynamics of excimer formation, excimer migration, and excimer dissociation in β-9,10-dichloroanthracene crystals were investigated by means of picosecond time-resolved fluorescence spectroscopy. In the temperature range from T = 20 K to T = 40 K we were able to temporally resolve the relaxation into the excimer state. The excimer formation rates were determined to be k ≈ 1.8 × 1011 s?1 at T = 40 K and k ≈ 2.0 × 1010 s?1 at T<30 K. The excimer migration was investigated by measuring the excimer annihilation rate as a function of temperature. At room temperature 20% of the excimers are dissociated. The excimer binding energy is estimated to be B = 1360 cm?1. The experimental results are explained in terms of a kinetic scheme comprising the population and depopulation of exciton, trap, and excimer states. The nature of the trap state is identified and it is shown that thermal activation of a 25 cm?1 librational mode induces the relaxation of the trap into the excimer state. 相似文献
20.
The thermodynamic parameters (log K, ΔG, ΔH and ΔS) of complexation of Eu(III), a chemical analogue of trivalent actinides, with pyridine monocarboxylates, namely, picolinic acid (pyridine-2-carboxylic acid), nicotinic acid (pyridine-3-carboxylic acid), isonicotinic acid (pyridine-4-carboxylic acid) have been studied at 1.0 M ionic strength adjusted by NaClO4 and 298 K by potentiometry, fluorescence spectroscopy and calorimetry. The potentiometric results revealed formation of four complexes, MLi (i = 1–4) in case of picolinate whereas only ML complexes in case of nicotinate and isonicotinate. The log KML for Eu(III) picolinate complex is higher than that for complexes of Eu(III) with the other two acids. The complexation reaction between Eu(III) and picolinate was found to be exothermic due to chelate formation via pyridyl nitrogen. In case of complexation of Eu(III) with nicotinate and isonicotinate, the enthalpy changes are similar as in the case of simple mono carboxylates and are positive. Life time measurements by time resolved fluorescence spectroscopy, for the decay of 5D0 state of Eu(III) also indicated the formation of ML4 with picolinate and formation of ML only with the other two acids. The experimental observations on the stability and binding mode of the complexes are corroborated by theoretical calculations using the TURBOMOLE software. The detail analysis of calculated charge values of the free ligands and the complexes indicates that charge polarization is more in the isonicotinate than in nicotinate upon complexation. 相似文献