水杨酸-2′-乙基己基酯在胶束中的增溶位点

考察了阳离子、非离子和阴离子表面活性剂存在下水杨酸-2′-乙基己基酯(EHS)的吸收光谱和激发态分子内质子转移(ESIPT)荧光光谱.结果表明,EHS可增溶在胶束中,2′-乙基己基碳链朝向胶束内核,而水杨酸基朝向胶束-水界面;胶柬环境有利于EHS分子对紫外光的吸收和分子内氢键的形成,从而使ESIPT荧光显著增强,激发态分子以发射可见光和非辐射去活化方式衰减;并根据EHS和表面活性剂分子的结构和大小,解释了EHS分子在胶束中的结合位点,荧光猝灭和酯水解的光谱测量进一步为此结合位点提供了佐证.     

Location of Solubilization of 2′-ethylhexyl Salicylate in Micelles

Absorption and excited state intramolecular proton transfer (ESIPT) fluorescence of 2′-ethylhexyl salicylate (EHS) were examined in the presence of cationic, non-ionic, and anionic surfactants. It was found that linear EHS molecule was solubilized in micelles with its flexible and hydrophobic 2′-ethylhexyl chain toward the micellar core and with its rigid salicyl moiety toward the micelle-water interface. The UV absorption of EHS was improved and the intramolecular hydrogen bonding formation of EHS was favored, resulting in greatly enhanced ESIPT fluorescence. The excited EHS molecules decay via visible luminescence and non-radiative deactivation. The binding sites of EHS in micelles were explained at a molecular level in terms of molecular structures and sizes of EHS and surfactants. Dynamic fluorescence quenching and spectral measurements of ester hydrolysis of EHS provide further evidences for the binding sites of EHS in different micelles.     

水杨酸-2’-乙基己基酯在胶束中的增溶位点

考察了阳离子、非离子和阴离子表面活性剂存在下水杨酸-2’-乙基己基酯(EHS)的吸收光谱和激发态分子内质子转移(ESIPT)荧光光谱. 结果表明, EHS可增溶在胶束中, 2’-乙基己基碳链朝向胶束内核, 而水杨酸基朝向胶束-水界面; 胶束环境有利于EHS分子对紫外光的吸收和分子内氢键的形成, 从而使ESIPT 荧光显著增强, 激发态分子以发射可见光和非辐射去活化方式衰减; 并根据EHS和表面活性剂分子的结构和大小, 解释了EHS分子在胶束中的结合位点, 荧光猝灭和酯水解的光谱测量进一步为此结合位点提供了佐证.     

Application of Polymer-Embedded Tris(2,2′ Bipyridine-Ruthenium(II) to Photodetection of Oxygen

A Nafion film containing tris(2,2′-bipyridine)ruthenium(II) as a luminescence probe was applied to photodetection of oxygen in a gas by utilizing the luminescence quenching by dioxygen. The linear Stern-Volmer plots of the emission intensity with respect to the oxygen concentration allowed quantitative determination of the oxygen. From the emission decay studied by a single-photon counting method, it was concluded that the quenching of the excited state Ru complex by oxygen proceeds by a conventional dynamic mechanism.     

Luminescence quenching of tris(2,2'-bipyridine)ruthenium(II) by 2,6-dimethylphenol and 4-bromo-2,6-dimethylphenol in sol-gel-processed silicate thin films

The luminescence properties of tris(1,2-bipyridine)ruthenium(II) (Ru(bpy)(3)(2+)), included in different organically modified silicate gel matrixes were investigated. Spin and dip-coated thin films were prepared from methyltrimethoxysilane (MTMOS) and methyltriethoxysilane (MTEOS). A blue shift in the emission spectrum of the MLCT excited state of Ru(bpy)(3)(2+) with respect to the aqueous solution was observed in all the films, practically independent of the reaction pH used to prepare the "sol," silane-derived precursor, and procedure used (dip-coating or spin-coating) to obtain the film. A bimodal distribution of probe sites in the films was obtained from modeling of the emission decays by a double exponential and from application of the exponential series method. The parameters of the decay components depended principally on the thermal treatment used in the processing of the films. The lifetimes decreased with the increase in the drying temperature of the films; at the same time, the emission spectra showed a red shift and the luminescence efficiency decreased. A luminescence quenching of the ruthenium complex in the films by 4-bromo-2,6-dimethylphenol and 2,6-dimethylphenol in aerated aqueous solution at pH 12 in contact with the film was also observed. The quenching plots obtained from luminescence intensities or luminescence intensity decay measurements showed a downward curvature. These plots could be fitted satisfactorily by a sum of two Stern-Volmer terms with quenching constants K(SV1) and K(SV2) associated with two different binding sites of the ruthenium complex. This result is indicative of the matrix microheterogeneity in the films and is fully consistent with the biexponential nature of the luminescence intensity decay profiles. The Stern-Volmer parameter values for both sites in the films suggest that only a low percentage of the probe is accessible to the quencher and its respective constant K(SV1) is lower than in water.     

Radiative and non-radiative decay processes of the excited state of the colored form of photochromic furylfulgide

The time evolution of the luminescence of the colored form of a furylfulgide dispersed at various concentrations in a poly(methyl methacrylate) film was measured as a function of the luminescence photon energy. The observed decay time of the luminescence is about 1–2 ns and one order of magnitude shorter than the radiative lifetime (14 ns) estimated from the absorption intensity. The decay time is independent of temperature below 77 K. These results suggest that the non-radiative tunneling process from the excited state to the ground state is responsible for the decay.     

DELAYED MICROSECOND LUMINESCENCE OF PHYCOBILISOMES

The time-resolved luminescence spectra (in the microsecond range) of phycobilisomes and biliproteins in buffer and polymer matrix were measured in the temperature range from 8 K. to 293 K. Delayed luminescence located in the same spectral region as prompt fluorescence of investigated samples (DLF) and the long-wavelength delayed emission in the720–760 nm range (DL1) was observed. The temperature and viscosity dependencies of DLF and DL1 luminescences were different, but both do not have uniexponential decays and are not quenched by oxygen. This means that delayed luminescence could be generated without the participation of the triplet states, or the chromophores could be shielded by protein against interaction with oxygen. The linear dependence of delayed luminescence on exciting light intensity shows that delayed luminescence is monophotonically induced. It seems that both DLF and DL1 are related to electron-cation recombination, which yields excited singlet states. The DLF is emitted from the first excited singlet state of biliprotein chromophores and DL1 from the same state of the excimers or from the triplet state of some groups of chromophores. Ionization energy of chromophores can be lowered as a result of their interactions with the environment. Delay of emission is due to the trapping or solvation of electrons. Every type of biliprotein consisting of phycobilisomes possesses its own “trap” and can emit the DL. In the case of native phycobilisomes a competition between the excitation energy trapping and transfer occurs.     

A radioluminescence study of a glassy matrix in the nanosecond time range

The luminescence of the scintillator bPBD excited by - and β-particles in a methylcyclohexane glass is studied at 77 K. In the time range 1–500 ns different luminescence decay laws are observed, showing the importance of track effects.     

Uranyl luminescence decay in phosphoric acid solution

Uranyl luminescences in phosphoric acid system has been studied. Uranyl excited by a nitrogen laser shows single or biexponential luminescence decays in the phosphoric acid system. When the uranyl ion or phosphoric acid concentration are lower, a single exponential luminescence decay appears, whereas at higher uranyl ion or phosphoric acid concentrations, biexponential decay is observed. Time-resolved spectra of uranyl in this system are measured. The reasons of the phenomena are tentatively established.     

配位体 SO_4~(2-)对激发态铀(Ⅵ)去活化的影响

近年来,随着激光、微弱信号测量以及瞬态测量技术等发展,对溶液中激发态离子的化学和物理行为的研究已日益受到人们的重视,激发态铀酰离子发光衰减的研究尤为活跃.Marcantonatos 等、Formosinho 等以及郑企克、王志麟等对高氯酸溶液中激发态铀酰离子的发光衰减过程进行了详细的研究.探讨了ClO_4~-溶液中pH 等对激发态铀酰离子的发光衰减的影响,观察到了一定的pH 条件下激发态铀(Ⅵ)的非单一指数衰减,并各自提出了不同的解释.值得提出的是,上述的一系列研究都是在高氯酸溶液中,其它体系中铀(Ⅵ)的发光哀减的研究进行得很少,报导则更少.1983年Joshi 等曾研究了80K 时SO_4~(2-)     

Temperature effect on the fluorescence anisotropy decay dynamics of Coumarin-153 dye in Triton-X-100 and Brij-35 micellar solutions

The fluorescence anisotropy decay dynamics of the fluorescent probe Coumarin-153 (C153) have been investigated in two neutral micelles, Triton-X-100 (TX-100) and Brij-35 (BJ-35), at different temperatures and analyzed on the basis of the well-known two-step model. Because steady-state fluorescence spectra of the above probe do not show any noticeable changes with respect to temperature, for either of the studied micelles, suggests a similar polarity in the microenvironment around the probe at all the temperatures studied. The anisotropy results indicated that, for both the micelles, the fluidity inside the Palisade layer increases with temperature. However, the temperature effect on the anisotropy decay is relatively more pronounced in TX-100 than in BJ-35. It is inferred that the temperature effect on the anisotropy decay in the BJ-35 micelle is mainly due to the thermal effect on the microviscosity in the micellar phase. In the case of TX-100, the results indicate that, along with the above thermal effect, an additional effect is observed due to the increased size and hydration of the micelle with temperature, with the result being that the fluorescence anisotropy decay in TX-100 is more sensitive to temperature than in BJ-35. In the TX-100 micelle, our studies show that with an increase in temperature, even though the micellar size increases substantially, the distance of the probe from the micellar core does not increase that significantly. Thus, with increasing temperature, the probe undergoes a relative migration toward the micellar core to avoid the increased hydration in the micellar Palisade layer.     

THE EFFECT OF ALIPHATIC ALCOHOLS ON FLUORESCENCE QUENCHING AND FLUORESCENCE POLARIZATION OF LUMINESCENCE PROBES IN HEXADECYLTRIMETHYLAMMONIUM BROMIDE MICELLES

Abstract— The fluorescence quenching of the indole chromophore by NO⁻₂ and the fluorescence depolarization of several luminescence probes in aqueous solutions containing hexadecyltrimethylammonium bromide (HDTBr) were measured as a function of added C₂–C₄ aliphatic alcohol concentration. The fluorescence decay profiles of pyrene in the micellar solutions were also measured to estimate the aggregation number of the micelles. The addition of n -butyl alcohol significantly reduces the fluorescence quenching rate and the aggregation number and increases the extent of fluorescence depolarization in HDTBr micellar systems. The addition of ethyl alcohol shows a similar but smaller effect.     

Dynamics and prototropic reactivity of electronically excited states in simple surfactant aggregates

Excitation of a molecule from the ground state to an electronically excited state can cause changes in its geometry, dipole moment, acidity or basicity, redox potentials and solvation. Bimolecular quenching of the excited state of the probe by other molecules present in the medium can be used to determine the mobilities of molecules and estimate microviscosities and encounter probabilities in the medium. Differences in excited state acidity or basicity relative to the ground state can be employed to investigate the dynamics of ultrafast proton transfer reactions. Three areas of current interest where fluorescent probes have served to elucidate important dynamic processes of molecules in simple self-aggregating surfactant systems such as aqueous micelles and reverse micelles are considered: (a) bimolecular quenching of excited states; (b) the dynamics of solvation of excited states and (c) ultrafast intermolecular excited state proton transfer (ESPT) reactions.     

Appearance of pure fluorocarbon micelles surveyed by fluorescence quenching of amphiphilic quinoline derivatives in fluorocarbon and hydrocarbon surfactant mixtures

A halide-sensitive fluorescence probe was utilized to evaluate the miscibility of fluorocarbon and hydrocarbon surfactants in aqueous micellar systems. The fluorescence of 6-methoxy-N-1,1,2,2-tetrahydroheptadecafluorodecylquinolinium chloride, FC10MQ, was quenched by halide ions dissociated from the surfactant. The fluorescence in micellar solutions showed an initially rapid decay. This suggests that halide ions effectively quench FC10MQ fluorescence at the micellar surface. The subsequent slow decay corresponds to the quenching of FC10MQ fluorescence in the aqueous bulk phase by the free counterions. The Stern-Volmer plots for fluorescence quenching gave a distinct break at the critical micelle concentration of the cationic surfactants. The abrupt increase in fluorescence quenching is attributed to the solubilization of the probe in the micelles. The fluorescence quenching behavior provides direct information about the immiscibility of fluorocarbon and hydrocarbon species in micelles, and the results indicate that almost pure fluorocarbon micelles appear in surfactants mixtures.     

Photoluminescence of <Emphasis Type="Italic">trans</Emphasis>-1,2-Di(2-naphthyl)ethylene: Conformation Isomerism and Validity of the Kennard Relation

trans-1,2-Di(2-naphthyl)ethylene (DNE) exists in liquid solutions as a mixture of three conformers which have relatively high stability in the excited state, do not convert into each other during the excited state lifetime, and thus behave as individual compounds. This behavior results in the dependence of the luminescence spectrum on the excitation wavelength and in nonexponential luminescence decay. Recently, it has been shown theoretically that the Kennard relation should hold for the excitation–emission matrix in the case of any luminophore in the thermodynamically equilibrium state independent of complexity of the luminescence properties. It has been experimentally shown in this study that the Kennard relation does hold for DNE solutions.     

A long-lived luminescence and EPR bimodal lanthanide-based probe for free radicals

We developed a novel spin-labeled terbium complex Tb(3+)/cs124-DTPA-TEMPO (1) by covalently labeling a nitroxide radical on the terbium complex for monitoring free radicals of various areas. This lanthanide complex probe shows a high EPR signal which resulted from the nitroxide radical moiety, and is weakly luminescent which resulted from the intramolecular quenching effect of the nitroxide radical on sensitised terbium luminescence. The intensity of both the EPR and luminescence can be modulated by eliminating the paramagnetism of the nitroxide radical through recognition of a carbon-centered radical analyte and thus gives a quantification of the analyte. We have preliminarily applied this probe in the luminescent detection of model carbon-centered radicals and hydroxyl radicals (·OH). This probe is water-soluble and contains lanthanide-luminescence properties, favorable for the time-resolved luminescence technique. The investigation of the intramolecular quenching process has showed that the labeled nitroxide radical quenches multiple excited states of the terbium complex, resulting in highly efficient quenching of terbium luminescence. This probe is the first example of intramolecular modulation of lanthanide luminescence by a nitroxide radical.     

THE PHOTOSENSITIZED FORMATION AND REACTION OF SINGLET OXYGEN, O2*(1Δ), IN AQUEOUS MICELLAR SYSTEMS

Abstract— Oxygenated aqueous solutions of methylene blue containing dispersions of sodium dodecyl sulphate micelles with solubilised diphenyl isobenzofuran were irradiated with red light and the rate of loss of furan was followed over several min. The results are consistent with a mechanism in which singlet oxygen is produced by energy transfer from methylene blue triplet in the aqueous phase, and then diffuses to and penetrates the interior of the micelles where it reacts with the furan. The competition between this process and the natural decay of the excited oxygen has been examined and a β-value of 9.7 times 10^-5 M determined which is comparable to that for the same reaction in homogeneous solvents. A model of the system is proposed and its kinetic features discussed.     

A ruthenium probe for cell viability measurement using flow cytometry, confocal microscopy and time-resolved luminescence

The capability of the new luminescent probe (dibenzo[h,j] dipyrido[3,2-a:2',3'-c]phenazine)bis(2,2'-bipyridine)ruthenium(II) dication, (RB2Z), to discriminate live and dead cells has been tested on rat hepatocytes and mouse lymphocytes. RB2Z-stained cells were analyzed using flow cytometry, fluorescence (confocal) microscopy and time-resolved luminescence measurements. The established viability probes propidium iodide (PI) and SYTOX green (SG) were used as controls. The intense luminescence of RB2Z at 606 nm is localized in the nucleus of nonviable cells. Viability measurements by flow cytometry and fluorescence microscopy using RB2Z as dead-cell marker yield the same results as PI and SG. The luminescence lifetime of RB2Z also displays sensitivity to cell viability (0.45 and 0.82 microsecond in presence of fully viable and dead cells, respectively). This ruthenium complex is photostable under laser sources and its 200 nm Stokes shift facilitates multicolor labeling experiments in flow cytometry and fluorescence microscopy. Unlike the currently available probes, the long-lived excited state of RB2Z also allows assays based on luminescence decay measurements.