Electrogenerated chemiluminescence quenching of Ru(bpy)3 2+ (bpy=2,2′-bipyridine) in the presence of acetaminophen,salicylic acid and their metabolites

Quenching of Ru(bpy) ₃²⁺ (bpy=2,2′-bipyridine) coreactant electrogenerated chemiluminescence (ECL) has been observed in the presence of acetaminophen, salicylic acid and related complexes. However, no quenching is observed with the acetylsalicylic acid. In most instances, quenching is observed with 100-fold excess of quencher (compared to ECL luminophore) with complete quenching observed between 10,000 and 100,000 fold excess. Fluorescence and UV–vis experiments coupled with bulk electrolysis support the formation of benzoquinone products upon electrochemical oxidation. The mechanism of quenching may involve the interaction of the electrochemically generated benzoquinone species with (i) the ^?Ru(bpy)₃²⁺ excited state or (ii) highly energetic coreactant radicals.     

The influence of temperature and dynamic quenching on the properties of 3-hydroxyflavone excited states

The influence of temperature and dynamic quenching on the properties of excited states of the normal and tautomeric 3-hydoxyflavone forms was studied. The stationary two-band fluorescence spectra of this luminophore in acetonitrile were recorded and analyzed. The spectra were observed under excitation by electromagnetic radiation in the region of the S ₁ absorption band over the temperature range 20–80°C. TEMPO was used as a quencher of the excited state. Heating caused temperature quenching of luminescence, and the tautomer formed via the excited state of the normal form of the luminophore was quenched more strongly both in pure solvent and in the presence of the quencher. An analysis of two-band fluorescence parameters led us to conclude that solution heating over the temperature range studied increased the rate of proton transfer by 1.25 times. The introduction of the quencher also accelerated proton transfer by 1.16–1.25 times as the temperature increased from room temperature to 80°C.     

Quenching of excited complexes by Fe-octaethylporphin in triplet-triplet annihilation of Mg-phthalocyanine in liquid solutions

The effect of triplet-state quenchers on the kinetics of triplet-triplet annihilation (TTA) of Mg-phthalocyanine (Mg-Phc) is studied. It is found that the rate constant of triplet-state quenching caused by TTA increases with increasing concentration [Q] of quenchers. The maximum values of the relaxation parameter of triplet states are proportional to [Q]². The experimental data correspond to TTA with the formation of TT complexes from molecules in triplet states. The proportionality of the decay rate of TT complexes into molecules in the ground state to [Q]² suggests that two quenching molecules are required for quenching one TT complex. It seems that the complex contains two locally excited triplet states of individual molecules. The spin correlation time in the triplet state seems to be longer than the average lifetime of complexes (≤10^?4 s). The quenching probability of triplet states in complexes (caused, in particular, by the energy of charge transfer) is lower than the probability of intermolecular triplet energy transfer to the quencher levels.     

Dynamic quenching of the dual fluorescence of molecules

Mathematical relations describing the properties of spontaneous steady-state dual fluorescence under conditions of dynamic quenching of excited states by foreign impurities are derived. It is shown that, in the case of a kinetic character of the reaction, the initial form of the dye and its photoproduct are quenched, the intensity ratio of the fluorescence bands of the initial form and the product linearly increasing with the quencher concentration. Analysis performed is applicable to a wide range of photoreactions accompanied by the dual fluorescence (charge transfer, proton transfer, complexation, etc.). The properties of the fluorescence, absorption, and dual fluorescence excitation for 3-hydroxyflavone in acetonitrile under conditions of dynamic quenching by the TEMPO spin quencher with a concentration below 1.25 × 10^?2 M are studied. 3-Hydroxyflavone is characterized by the excited-state intramolecular proton transfer and by the fluorescence spectrum consisting of two well-spaced bands. The observed dependences of the intensity of both fluorescence bands on the quencher concentration correspond to the theoretical conclusions. The Stern-Volmer constants calculated from the experimental data on the assumption of diffusion quenching of the excited states are 858 and 1141 M^?1 for the normal and tautomeric fluorescence bands, respectively. The experimental results reveal the kinetic character of the excited-state proton transfer in 3-hydroxyflavone in acetonitrile.     

Studying reactions that proceed from highest excited states of molecules using fluorescence quenching

The steady-state monochromatic excitation of a luminophore that has fluorescing products is considered. The effect of dynamic quenching of highest excited states on the fluorescence of singlet states under its excitation via singlet S ₁ and S _n (n ≥ 2) states is discussed. It is shown that the use of the method of fluorescence dynamic quenching by foreign impurities opens new possibilities for studying photoreactions that proceed via S _n singlet states. A large number of primary photoprocesses are considered which include the electron density redistribution (the internal electron transfer) in the excited state, protolytic reactions, intramolecular proton transfer (phototautomerization), hydrogen bonding, and formation of excimers and exciplexes. It is shown that, upon dynamic quenching, the bimolecular quenching constant of an excited level depends on the amount of thermal energy released in the luminophore before the occurrence of the light emission event. Based on the experimental measurements of the fluorescence spectra at different quencher contents, the calculation of the Stern-Volmer constant for reaction products is considered in detail. It is shown that this constant can be most reliably determined from the dependence of the fluorescence intensity ratio of the initial reagents and the quencher product rather than from the dependence of the fluorescence intensity of the products on the concentration of the quencher. The relations determined are used in analysis of the experimental fluorescence spectra of solutions of 3-hydroxyflavone excited by radiation with different wavelengths lying in the range of the S ₁ and S ₂ absorption bands. The temperature behavior of the Stern-Volmer constant for different fluorescence bands of 3-hydroxyflavone is considered. It is shown that, if these constants for the normal and tautomeric forms are correctly determined, their temperature dependences are similar.     

Dynamic fluorescence quenching and the highest excited states of molecules

The dynamic fluorescence quenching in organic molecules, or quenching of the second kind according to Vavilov’s classification, is an efficient method of investigating excited states in solutions and is widely used in various fields. The effect of quenching on the intensity of the fluorescence from the first and higher singlet states of organic molecules is studied. The results may serve as a basis for determining the nature of the short-wavelength luminescence and can be used to distinguish the S _n fluorescence from the comparably intense luminescence of impurities, which is a very important problem when investigating such emissions. A method for obtaining dynamic quenching by specially chosen quenchers is proposed. The method is based on an experimentally found strong increase in the constants of bimolecular collisions of luminophore and quencher molecules when the luminophore is excited through the highest singlet states.     

Ground- and excited-state spectroscopic studies on [1-(4-methoxyphenyl)-3-(amino)-2,4-(dicyano)-9,10-tetrahydrophenanthrene]

The effects of polar and nonpolar solvents on both the ground and the excited-state properties of [1-(4-methoxyphenyl)-3-(amino)-2,4-(dicyano)-9,10-tetrahydrophenanthrene] is examined. Light absorption results in a population of a locally excited (LE) first singlet state (S₁,n^*) which shows sensitivity to the polarity of the surrounding solvent and hydrogen-bonding ability to the quencher 4-methylpyridine. Relaxation of this state leads to an intramolecular charge-transfer state (ICT) which leads to a large Stokes shift in polar solvents and an excited-state dipole moment of _e= 10D. The quenching of the fluorescence state by 4-methylpyridine studied inn-hexane and acetonitrile at room temperature is found to be efficient and a positive deviation from linearity was observed in the Stern-Volmer plots even at concentrations of 4-methylpyridine below 0.4M. This is explained as a result of the occurrence of both a dynamic and a static quenching mechanism. The static quenching constants (K _sv) along with those obtained by visible spectroscopy (K _GS) indicate that the ground-state complex is weak and relatively solvent dependent.     

Determination of the stern-volmer constant in quantum systems with dual fluorescence

The mathematical relations describing the properties of the steady-state spontaneous emission of quantum systems with dual fluorescence under conditions of dynamic quenching of excited states by foreign impurities are analyzed. The direct dependence of the intensity and yield of the photoproduct fluorescence on the quencher concentration is not simple and cannot serve as a convenient base for determining the Stern-Volmer constant. It is shown that, in the case of a kinetic character of product formation, the fluorescence intensity ratio of the initial dye and its photoproduct linearly increases with the quencher concentration. The relation obtained can be used to determine the constant of bimolecular quenching of the excited states of reaction products. This conclusion is based on the analysis of the experimental fluorescence spectra of 3-hydroxyflavone, obtained upon excitation in the region of the S ₁ absorption band under conditions of dynamic quenching by potassium iodide. This analysis can be applied to a wide range of luminophores with photoreactions accompanied by dual fluorescence (charge transfer, proton transfer, phosphorescence, complexation, etc.).     

Quenching effects in flashlamp-excited polymethine dye lasers

The main action of oxygen dissolved in air-saturated polymethine-dye laser solutions is the quenching of the excited singlet state by enhancing transitions between it and the triplet state. A substantial increase of laser efficiency was observed by outgasing the solutions of five di- and tri-carbocyanine dyes. In one case (DOTC) a specific triplet state quencher (COT) was found.     

Determination of the Constants of Binding of Acridine Dyes with Micelles of Sodium Dodecyl Sulfate Using the Quenching of Delayed Fluorescence by Heavy Atoms

The constants of binding dye molecules with the micelles of sodium dodecyl sulfate are determined using quenching of delayed fluorescence of acridine dyes by sodium iodide in aqueous–micellar solutions. Kinetic equations have been composed that describe the processes of deactivation of the excited states of dyes. By solving these equations at the concentration of the quencher sodium iodide corresponding to the minimum lifetime of triplet states and at the concentration of micelles corresponding to the least value of the delayed fluorescence quenching rate constants, we obtained the constants of binding dyes with micelles equal to 1.3·10⁷, 2.9·10⁷, and 3.1·10⁷ M^–1 for trypaflavine, acridine orange, and acridine yellow, respectively. We calculated the rate constants of quenching of the triplet states of the molecules of dyes by iodide ions (I ^–) that decreased in transition from trypaflavine to acridine orange and acridine yellow.     

Investigation of excited-state proton transfer in 3-hydroxyflavone molecules

The dual fluorescence spectra of 3-hydroxyflavone molecules excited by electromagnetic radiation in the region of the S ₁ and S ₂ absorption bands in the temperature region of 20–80°C are studied using the dynamic quenching of the excited state. An analysis of the fluorescence parameters shows that heating the solution from room temperature to 60°C increases the proton transfer rate by a factor of 1.24 in the case of standard excitation into the main absorption band and even stronger (by a factor of 6.9) in the case of excitation into the second absorption band. The presence of a quencher reduces the yield of the two emission bands and noticeably increases the proton transfer rate, by a factor of 1.16 at room temperature and by a factor of 1.25 at 80°C. Upon excitation into the second singlet band, the transfer rate increases even more (especially at higher temperatures), by a factors of 1.24 and 3.5 for the same temperatures. The temperature dependences of the transfer rate constant allowed us to estimate the activation energies of the proton transfer reaction under different physical conditions and reach conclusions about the mechanism by which this reaction proceeds. It is found that the proton transfer activation energy decreases from 500 to 360 cm⁻¹ when measured in temperature ranges of 20–40 and 20–60°C. The introduction of a quencher with a concentration of 5 × 10⁻³ M increases the activation barrier to 534 and 471 cm⁻¹ in the same temperature ranges.     

Determination of the rate constant of oxygen quenching of the excited states of molecules from the singlet oxygen luminescence

We have pioneered a method of determining the rate constant of quenching of the excited electronic states of molecules by molecular oxygen from measurements of the kinetics of photosensitized luminescence of singlet molecular oxygen (^lδ_g). The method can be used in the case where the lifetime of the excited electronic state in an air-saturated solution is comparable with or larger than the luminescence time of the singlet molecular oxygen in the given solvent. It is shown that this situation is implemented on quenching, by molecular oxygen, of the excited triplet states associated with the biopolymers of tetrapyrrole molecules in aqueous (H₂O and D₂O) solutions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 3, pp. 401–404, May–June, 2000.     

Effect of temperature on the dynamic quenching of the dual fluorescence of molecules

The properties of the dual fluorescence of 3-hydroxyflavone in acetonitrile are studied under conditions of dynamic quenching by the spin quencher TEMPO in the temperature range from 20 to 80°C. 3-Hydroxyflavone is characterized by the intramolecular excited state proton transfer and its spectrum consists of two well-spaced fluorescence bands belonging to the normal and tautomeric forms. The fluorescence was selectively excited at wavelengths of 290, 304, and 340 nm, belonging to different absorption bands of the luminophore. The character and degree of the temperature quenching of the fluorescence depend on the excitation wavelength and are considerably different for normal and tautomeric fluorescence bands. The Stern-Volmer constants for both forms, calculated from the experimental data on the assumption of the diffusion mechanism of quenching of the excited states, increase with temperature. Both in the pure solutions and in the solutions with the quencher, the intensity ratio of the fluorescence of the initial form and the product increases with heating in the entire temperature range from 20 to 80°C for all the above excitation wavelengths. Original Russian Text ? V.I. Tomin, 2008, published in Optika i Spektroskopiya, 2008, Vol. 104, No. 6, pp. 926–933.     

Quenching of Lanthanide Emission by Intervalence Charge Transfer in Crystals Containing Closed Shell Transition Metal Ions

The quenching of the luminescence originating from the excited states ³P₀ and ¹D₂ of Pr³⁺ and ⁵D₃ and ⁵D₄ of Tb³⁺ has been studied in oxide crystals containing closed shell transition metal ions, such as titanates, vanadates, niobates, and tantalates. It has been shown that the emission from these excited states can be quenched by an intervalence charge transfer mechanism. The temperature dependence of the emission intensities has allowed estimating indicative activation energies for the crossover to the intervalence charge transfer state. In the case of Tb³⁺, the quenching gives rise to relatively short decay times for the ⁵D₄ state.     

Viscosity Effect Study on Quenching of Photoinduced Excited Triplet Duroquinone by TEMPO

ABSTRACT

Quenching dynamics of excited quinone molecules are given much attention in photochemistry and biochemistry. In order to study the viscosity effect on the quenching of triplet excited state of duroquinone (³DQ?) by stable radical, 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO), this study measured chemically induced dynamic electron polarization (CIDEP) spectra and transient absorptive spectra in various solvents. The solvents used were ethylene glycol, 1,2-propanol and their mixtures with different ratio in volume. The Stern-Volmer plot was obtained form CIDEP spectra of photolysis of DQ with different TEMPO concentrations. Combining the slope of the Stern-Volmer plot with lifetime of ³DQ?, determined from the ³DQ? transient absorbance decay curve, the quenching rate constants of ³DQ? by TEMPO were calculated in each solvent. The results indicate that the quenching rate constant is viscosity-dependent, and that it decreases linearly with the increase in solvent viscosity in the range used in our experiment.     

Study of the Interaction Between Apis mellifera Venom and Micro-Heterogeneous Systems

The bee venom, used in treatment of inflammatory and articular diseases, is a complex mixture of peptides and enzymes and the presence of tryptophan allows the investigation by fluorescence techniques. Steady state and time-resolved fluorescence spectroscopy were used to study the interaction between bee venom extracted from Apis mellifera and three micro heterogeneous systems: sodium dodecylsulphate (SDS) micelles, sodium dodecylsulphate-poly(ethylene oxide) (SDS-PEO) aggregates, and the polymeric micelles LUTROL^® F127, formed by poly(ethylene oxide)-poly(propylene oxide)- poly(ethylene oxide). Fluorescence parameters in buffer solution were typical of peptides containing tryptophan exposed to the aqueous medium, and they gradually changed upon the addition of surfactant and polymeric micelles, demonstrating the interaction of the peptides with the micro heterogeneous systems. Quenching experiments were carried out using the N-alkylpyridinium ions (ethyl, hexyl, and dodecyl) as quenchers. In buffer solution the quenching has low efficiency and is independent of the alkyl chain length of the quencher. In the presence of the micro heterogeneous systems the extent of static and dynamic quenching enhanced, showing that both fluorophore and quenchers reside in the microvolume of the aggregates. The more hydrophobic quencher (dodecyl pyridinium ion) provides higher values for K _SV and dynamic quenching constants, and SDS-PEO aggregates are most efficient to promote interaction between peptides and alkyl pyridinium ions. The results proved that bee venon interacts with drug delivery micelles of the copolymer LUTROL^® F127.     

Sensitized Near-Infrared Luminescence From NdIII, YbIII and ErIII Complexes by Energy-Transfer From Ruthenium 1,3-Bis([1,10]Phenanthroline-[5,6-d]-Imidazol-2 -yl)Benzene

The luminescent ruthenium 1,3 -bis([1,10]phenanthroline-[5,6 -d]- imidazol-2 -yl)benzene (bpibH₂) complex, a potentially useful bridging ligand with a vacant diimine site, has been used as ‘metallo ligand’ to make heterodinuclear d–f complexes by attachment of a {Ln(dik)₃} fragment (dik?=?1,3-diketonate) at the vacant site. When Ln?=?Nd, Yb, or Er the lanthanide centre has low-energy f–f excited states capable of accepting energy from the ³MLCT excited state of the Ru(II) centre, there is quenching in the ³MLCT luminescence of the Ru(II) centre, that affords sensitized lanthanide(III) based luminescence in the near-IR region. Nd(III) was found to be the most effective at quenching the ³MLCT luminescence of the ruthenium component because of the high density of f–f excited states of the appropriate energy which make it as effective energy-acceptor compared to Er and Yb complexes.     

Wavelength Dependant Quenching of 2,5-Diphenyloxazole Fluorescence by Nucleotides

The quenching of 2,5-diphenyloxazole (PPO) fluorescence by nucleotides has been investigated by electronic absorption and steady state fluorescence spectra. Five purine nucleotides AMP, ADP, ATP, GMP and dGMP, one pyrimidine nucleotide UMP and one dinucleotide NAD have been employed in the present study. Electronic absorption studies indicate that there is no ground state complexation between the nucleotides and PPO. The quenching of PPO fluorescence was investigated at two different wavelengths. When excited at 304 nm, the λ _max of PPO, the fluorescence spectra of PPO is quenched following Stern–Volmer kinetics. The quenching ability of nucleotides are in the order NAD > AMP > ADP > GMP > dGMP > UMP. The K _SV and k _q values obtained indicate that AMP is a better quencher of PPO fluorescence than GMP, which is contrary to commonly observed pattern. The quenching is found to be dynamic in nature. However, when excited at 260 nm, the absorption maximum of the nucleotides, the fluorescence intensity of PPO is reduced with increase in the concentration of the nucleotide. This is attributed to the primary inner filter effect arising due to the absorption of the incident radiation by the nucleotides. Thus the inner filter effect phenomenon can be employed to assay the non-fluorescent molecules by fluorimetry.     

Statistical Meaning of the Excited-State Quenching Probability Found by a Fluorescence Depolarization Method

It is shown that the probability of quenching the excited electronic state of complex molecules, which is obtained from the vapor fluorescence depolarization, is averaged over the configurations of collisions with the quencher molecules with a collisional chaotization weight factor, i.e., it is transformed by this factor. The conditions under which this probability is close to the conventional one averaged only over the configurations of collisions are discussed. __________ Translated from Zhurnal Prikaldnoi Spektroskopii, Vol. 72, No. 4, pp. 563–564, July–August, 2005.     

Energy transfer in the A2Σ+ state of OH following v’ = 1 excitation in a low pressure CH4/O2-flame

2 Σ⁺(v’=1) level of OH. Measurements were performed in a laminar premixed flame at 10 Torr total pressure. The low pressure allowed the spatial variation of the effective quenching rate to be determined through the flame front. In addition, the dependence of the quenching rate on rotational quantum number was measured by exciting a series of rotational lines in the range N’=0–16. The results show that the total quenching rate decreases only 17% through the flame front, in the region where OH can be detected. Nevertheless, the absolute value of the quenching rate Q is required if absolute concentrations are to be determined from LIF-signals. The variation both of Q and of the rotational relaxation rate with excited rotational quantum state must be known for quantification of LIF-temperature measurements via the Boltzmann relation. Finally, the rotational and vibrational energy transfer (RET, VET), was investigated by recording the spectrally and temporally resolved fluorescence. For all excited rotational lines, efficient RET to neighbouring rotational states was observed, but only very little VET. Total RET rates were determined from the difference between the time-resolved broadband (total fluorescence) and narrowband (fluorescence from the laser excited level) curves. The experimental results were compared with simulations using a dynamic model, which describes the energy transfer for flame conditions. With the available input data (temperature, major species concentrations and collision-partner specific RET cross sections), good agreement was obtained. Received: 3 February 1997/Revised version: 3 September 1997