On the intramicellar fluorescence quenching rate constant in cylindrical micelles

A theoretical model developed for the intramicellar fluorescence quenching rate constant in spherical micelles is extended to cylindrical micelles for diffusion- and reaction-controlled processes. The rate constants for prolate ellipsoidal micelles are expected to be intermediate between those of spherical and those of cylindrical micelles of the same volume. The importance of diffusion transients is dicussed as a function of micellar shape and the fluorescence decay time of the excited probe.     

Pyrene fluorescence in the presence of nonquenching and dynamic quenching salting-out agents

A new, simple, and rapid method to determine Setschenow (i.e., salting-out) constants for luminescent organic compounds in aqueous solutions has been developed using steady-state and time-resolved fluorescence measurements. Application of the new method was demonstrated using pyrene in the presence of nonquenching (K⁺) and dynamically quenching (Cs⁺) akali metal chloride salt solutions at room temperature. For these two model systems, Setschenow constants for pyrene salting-out by KCl and CsCl were determined to be 0.211 and 0.355 M⁻¹, respectively. We expect that the methodology reported in this paper can be applied equally well to interactions between a variety of salting-out agents and fluorescent biological and/or environmental molecules in aqueous solutions.     

The refractive index correction to the radiative rate constant in fluorescence lifetime measurements

The dependence of fluorescence decay times upon the refractive index of the solvent has been measured in two types of system: (a) in a single solvent at different temperatures, (b) in different solvents. The results are consistent with an n² dependence of the radiative rate constant, as has been predicted theoretically.     

Quantitative structure-property relationship study on the determination of binding constant by fluorescence quenching

Models to predict binding constant (logK) to bovine serum albumin (BSA) should be very useful in the pharmaceutical industry to help speed up the design of new compounds, especially as far as pharmacokinetics is concerned. We present here an extensive list of logK binding constants for thirty-five compounds to BSA determined by florescence quenching from the literature. These data have allowed us the derivation of a quantitative structure-property relationship (QSPR) model to predict binding constants to BSA of compounds on the basis of their structure. A stepwise multiple linear regression (MLR) was performed to build the model. The statistical parameter provided by the MLR model (R = 0.9200, RMS = 0.3305) indicated satisfactory stability and predictive ability for the model. Using florescence quenching spectroscopy, we also experimentally determined the binding constants to BSA for two bioactive components in traditional Chinese medicines. Using the proposed model it was possible to predict the binding constants for each, which were in good agreement with the experimental results. This QSPR approach can contribute to a better understanding of structural factors of the compounds responsible for drug-protein interactions, and be useful in predicting the binding constants of other compounds.      

Enhanced conjugated polymer fluorescence quenching by dipyridinium-based quenchers in the presence of surfactant

Poly[(2-methoxy-5-propyloxysulfonate)phenylene vinylene] (MPS-PPV) was synthesized directly from its bischloromethylated monomer, considerably reducing the total number of steps involved in the polymer preparation. For the first time, a simple technique of ultracentrifugation was employed for final purification of the polymer. The interactions among the polymer, surfactant, and quencher molecules, as well as amplified fluorescence quenching and fluorescence enhancement associated with the interactions, were investigated and discussed. When compared with methyl viologen [MV]2+, higher values of Stern-Volmer constant K(SV) values on the order of > or =10(7) M(-1) were observed for the newly synthesized N-(2-carboxyhexadecanoyl)-N'-methyl-4,4'-bipyridinium iodide bromide ([CHMB]2+) quencher in the presence of 1,2-dioleoyl-3- trimethylammonium propane (DOTAP) surfactant. Comparisons of surfactants demonstrated that the K(SV) of [CHMB]2+ was 10-fold higher in the presence of dodecyltrimethylammonium bromide (DTAB) surfactant than with DOTAP. Polymer fluorescence was totally recovered upon addition of DOTAP surfactant to a MV-quenched polymer system, whereas only 50% of fluorescence was recovered upon addition of DOTAP surfactant to the CHMB-quenched polymer solution. In contrast, no fluorescence was recovered when DTAB was added to either the MV- or CHMB-quenched polymer systems. Thus, fluorescence enhancement was observed for the polymer complex with DOTAP, whereas fluorescence quenching was predominant in the polymer complex with DTAB. Such studies will not only help to better understand the intrinsic properties of the ionic conjugated polymer and amplified fluorescence quenching and enhancement but also provide guidelines to develop the next generation of ionic conjugated-polymer-based biosensors.     

The size of sodium dodecyl sulfate micelles in the presence ofn-alcohols as determined by fluorescence quenching measurements

The steady-state fluorescence quenching technique was used to investigate the effect of the presence of a series of alcohol homologues of mid-sized straight chain on the size of mixed micelles of sodium dodecyl sulfate (SDS). We used pyrene at concentration of ca. 10^–6M, where only its monomer exhibits any fluorescence, as fluorescent probe, and cetylpiridinium chloride at concentrations in the range (1–9)×10^–5 M as quencher. This technique allows one to determine the micellar aggregation number. The number of alcohol molecules per micelle was calculated from reported values for the micelle-water partition coefficient. On the assumption of spherical micelles, their hydrophobic radii was then calculated. The hypothesis that micelle size is determined by the available surface area per charged headgroup is discussed in the light of the results obtained.     

A discrete stochastic model of diffusion controlled reactions. The rate constant

Diffusion controlled chemical reaction is modelled as random walk on a cubic lattice. The rate coefficient is shown to depend on the spatial distribution of the reactants.

---

- . .

     

The quenching of chlorine fluorescence in the gas phase

Laser induced fluorescence has been observed from the B³Π(O⁺_u) state of chlorine. Lifetimes have been measured from 19 to 208 Pa, but the radiative lifetime is too long to be extracted from the data. A rate coefficient of 3.2 × 10[su13] cm³ mol?1 s?1 was measured for quenching by Cl₂ or Ar, the removal process being collision induced predissociation of the ³Π(O⁺_u) state.     

Transient processes of diffusion-controlled quenching of pyrene fluorescence on the surface of SiO2

Using the diffusion-controlled bimolecular reaction of quenching of pyrene fluorescence by N,N-dimethylaniline on the surface of thermally activated highly dispersed SiO₂ as an example it is shown that a transient non-steady-state process is observed in the initial section of the kinetics.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 30, No. 6, pp. 328–331, November–December, 1994.     

Marcus dependence of the fluorescence quenching constant of zinc tetraphenylporphin in isopropanol on the reduction potential of the oxidant

The quenching of the fluorescence of zinc tetraphenylporphin (ZnTPP) by oxidizing agents (quinones and nitro-compounds) in isopropanol) is based on a dynamic as well as on a static mechanism. Static quenching is caused by the formation of outer-sphere molecular complexes, in which the donor and the acceptor are joined by alcohol molecules. The dependence of the constant of static fluorescence quenching on the reduction potential of the oxidant is represented by a bell-shaped curve according to the classical theory of electron transfer.L. V. Pisarzhevskii Institute of Physical Chemistry, Ukrainian Academy of Sciences, Kiev. Translated from Teoretischeskaya i Éksperimental'naya Khimiya, Vol. 27, No. 6, pp. 689–695, November–December, 1991. Original article submitted February 27, 1989.     

Magnetic quenching of fluorescence

The direct and indirect mechanisms for the magnetic enhancement of radiationless decay processes are described, and used to account for the experimental observations of the magnetic quenching of fluorescence from carbon disulphide, glyoxal, and nitrogen dioxide.     

荧光猝灭法测定痕量亚硝酸根

基于在酸性介质中,NO-2与藏红T直接反应,使藏红T的荧光猝灭,加入强碱弱酸盐对体系有增敏作用,据此提出了荧光法测定痕量NO-2的新方法。方法的线性范围为2.8～294ng/mL,方法的检出限为2.8ng/mL。可直接用于水样及蔬菜中痕量NO-2的测定。     

On the relationship between the radiative rate constant and the fluorescence intensity in organic fluorophores

In this Letter we explore the relationship between the radiative constant, k_r, and the lineshape of an emission spectrum for fluorescent organic molecules, in particular tryptophan. We make a number of judicious approximations to the expression given by Strickler and Berg in conjunction with the log-normal function for the lineshape. Our result is a closed form expression for k_r in terms of the inverse maximum wavelength λ_max⁻¹ which compares well with recent experimental findings for tryptophan residues in proteins.     

The mechanism of riboflavin fluorescence quenching by nucleophiles

It is shown that the quenching of riboflavin (RF) fluorescence by nucleophiles, i.e., sulfite-, nitrite-, thiocyanate-, iodide-, and bromide ions, occurs by both a dynamic and static mechanism. The constants of quenching excited RF by anions and the constants of equilibrium of RF in the ground state and anions are determined. The formation of RF radicals in the presence of low concentrations of nucleophiles is revealed using flash photolysis.     

The rate constant for the intramolecular isomerization of pentyl radicals

The thermal decomposition of n-pentane has been investigated in the temperature range 737 to 923 K. Making various assumptions, the detailed distribution of major products (methane, ethane, ethene, propene, and 1-butene) is used to evaluate the rate constant for the unimolecular isomerization which proceeds via a five-membered, cyclic transition state. Two alternative sets of assumptions are used. Common to both of them are assumptions concerning the thermochemistry and rate constants for decomposition of the C₅H₁₁ radicals. Method 1 assumes that all secondary C? H bonds are equally reactive towards hydrogen abstraction in which case, in addition to the value of ??₁₀, the ratio of the rate constants for abstraction from primary and secondary C? H bonds is evaluated. Values about a factor of two higher than published values for similar molecules are obtained. The alternative, method 2, assumes that the ratio of abstraction from the 1- and 2- positions of n?pentane is the same as that published for n?butane, in which case, in addition to the value of ??₁₀, the ratio of the rates of abstraction from the 3- and 2- positions of n-pentane is obtained. The value obtained is 0.401 which is to be compared with the statistically expected (and assumed in method 1) 0.5. Detailed discussions of the values of ??₁₀ obtained leads to the conclusion that method 1 leads to the best value where θ = 2.303RT in kcal/mol and error limits are two standard deviations. Combination of this value with values recalculated from published lower temperature data gives which, it is concluded, is the best value in the range 438 to 923 K.     

荧光猝灭法测定壳聚糖含量

在pH 6.3的NaH2PO4-Na2HPO4缓冲溶液中,壳聚糖对荧光素的荧光强度具有明显的猝灭作用,且在一定浓度范围内,其猝灭程度与加入的壳聚糖浓度成线性关系,据此建立了一种新的测定壳聚糖含量的荧光猝灭分光光度法。该方法的回归方程为ΔF=64.02+42.28ρ(mg/L),R2=0.9942,线性范围为0.50~10.0 mg/L,检出限为0.27 mg/L。样品测定的RSD为4.5%(n=6),平均回收率为99.3%。采用该方法可测定复杂样品中的壳聚糖含量。     

Orientation effects in fluorescence quenching for adsorbed aromatic hydrocarbons

Fluorescence quenching by a potential electron donor or acceptor has been examined for an aromatic hydrocarbon adsorbed on aerosil, for which unusual temperature effects have been observed, where the process is dependent on the nature of the quencher. These phenomena are examined in terms of reaction stereospecificity. By this is meant the resultant displacement from a series of jumps between localization positions. Surface Chemistry Institute, Ukrainian National Academy of Sciences, Prospekt Nauki 31, 252039 Kiev, Ukraine. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 33, No. 1, pp. 12–16, January–February, 1997.     

A study of molecular diffusion in alcohol—water solution of poly-4-vinylpyridine by fluorescence quenching

Intra- and intermolecular diffusion processes in alcohol—water solutions of poly-4-vinylpyridine (PVPy) were studied by the fluorescence quenching method. It was prepared fluorescent-labelled PVPy (PVPy-F) by copolymerizing 4-vinylpyridine with anthrylmethylmethacrylate (F) (one chromophore group per 500 chain links in the copolymer). PVPy carrying both the chromophore and quenching chain links (quaternization of the pyridine residue by dimethylsulphate) (PVPy-FQ) and PVPy carrying only the quenchers (PVPy-Q).Measurement of the mean lifetime of the excited state of the anthracene group for the polymers and for the monomer analogue (F) with increasing quencher concentration and use of the Stern-Volmer relation permit determination of the constants of bimolecular collisions between the monomer quencher (Q) (4-ethyl-N-methyl pyridinium sulphate) and F, between the monomer quencher and PVPy-F and between Q and F incorporated in the same polymer chain (PVPy-FQ). The values of the diffusion constant for the system of PVPy-F and Q and for the system of PVPy-FQ are approximately two and four times respectively less than that for the monomer pair (F + Q). For the latter system, the finding indicates some hindrance to the diffusion of the chain links with each other within the coil. Nevertheless, their mobility remains high and probably microdiffusion will not limit chemical reactions of functional groups within coils and with monomer molecules.In studying the fluorescence quenching of the chromophore for PVPy-F in the presence of the polymer quencher, it was found that mutual interpenetration of the polymer coils is intensified markedly when the solution volume is filled entirely by the swelling coils.     

Oxygen diffusion in poly(dimethyl siloxane) using fluorescence quenching. II. Filled samples

The method of fluorescence quenching has been used to measure the transport properties of oxygen in poly(dimethyl siloxane) (PDMS) filled with small weight fractions of fumed silica. The experimental results show that the diffusion coefficient of oxygen and the pre-exponential term in the Arrhenius relationship are reduced, but the activation energy is not affected. In the pressure and temperature ranges used in these experiments, the diffusion coefficient was found to be independent of both the oxygen and fluorophor concentrations. A discussion concerning the effect of fillers on the pre-exponential term is presented.