Photoluminescence of a soluble polypyrrole based on N-vinylpyrrole

Photoluminescence of a novel polypyrrole based on N-vinylpyrrole was systematically observed in organic solutions. The polymer, which has a unique molecular structure, exhibited good photoluminescence in organic solutions. The emission peak of the polymer exhibited one strong green emission band at around 510 nm in common organic solutions. The maximum fluorescence quantum yield of the polymer was found to be 0.16 in NMP solution with fluorescein as standard. At the same concentration, the photoluminescence intensity increased in the order of CHCl₃, THF, DMSO, CH₂Cl₂ and NMP. The photoluminescence spectrum had a slight red shift as the polarity of the solvents increased. The photoluminescence intensity also increased with the polarity of the solvent, except DMSO. This is because of its hygroscopicity in air and its viscosity. In THF solutions, the photoluminescence intensity increased until the concentration reached a certain weight percent (3.0×10⁻² wt.%) and then decreased with higher concentrations. This was most likely due to quenching in the aggregate phase. Furthermore, iron ion was a quencher in the DMSO solution. In a mixed solvent system of DMSO and water, water showed a typical quenching effect.     

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.     

Effect of Solvent Polarity on Fluorescence Quenching of New Indole Derivatives by CCl4

ABSTRACT

The fluorescence quenching of solutes 3-[5′-methyl-3′-phenylindol-2′-yl]-s-triazolo [3,4-b] [1,3,4] thiadiazol-6(5H)-thione (MPITTT) and 3-phenyl-2,5-bis-[thiosemicarbazido] indole (PbisTI) by carbon tetrachloride (CCl₄) in dioxane and acetonitrile mixtures has been studied at room temperature by steady-state fluorescence measurements. The positive deviation from linearity has been observed in the Stern–Volmer (S-V) plots for both fluorophores in different composition of mixed solvents even at moderate CCl₄ concentration (0.10 mol dm^?3). Various quenching parameters of the quenching processes have been determined using the extended S-V equation and have been found to be dependent on the solvent polarity. Further, with the use of the finite sink approximation model, it is concluded that the bimolecular quenching reactions are diffusion limited, and the distance parameter R′ and mutual diffusion coefficient D are estimated independently.     

Fluorescence Quenching Studies of 1,3‐Diphenyl Benzene

Fluorescence quenching of 1,3‐diphenyl benzene (m‐terphenyl) by carbon tetrachloride (CCl₄) at steady state in different solvents, namely n‐hexane, n‐heptane, cyclohexane, toluene, benzene acetonitrile, 1,4‐dioxane, and with a transient method in benzene has been done at room temperature to understand the role of quenching mechanisms. The Stern–Volmer plot was found to be linear for all the solvents studied. The probability of quenching per encounter p was determined in all the solvents and was found to be less than unity. Further, from the studies of rate parameters and lifetime measurements in benzene at different temperatures (30–60°C), it was shown that the phenomenon of quenching is generally governed by the well‐known Stern–Volmer (S‐V) plot. The activation energy E _a (E′_a) of quenching was determined using literature values of activation energy of diffusion E _d, and it was found to be greater than E _d, which confirms the fact that the quenching mechanism is not solely due to material diffusion but there is also contribution from activation energy.     

High-temperature VUV spectroscopy of KYF4 crystals doped with Nd3+, Er3+ and Tm3+ ions

Thermal quenching of 5d-4f luminescence from Nd³⁺, Er³⁺ and Tm³⁺ ions doped into KYF₄ crystals has been investigated in the temperature range up to ∼750 K where this luminescence is completely quenched. The obtained temperatures of thermal quenching (T_q) are ∼270, 495, 450 K for Nd³⁺, Er³⁺, Tm³⁺, respectively. At high temperatures, thermal quenching of 5d-4f luminescence from Nd³⁺ and Er³⁺ is accompanied by the appearance of 4f-4f luminescence from the lower-energy 4f levels. It has been shown that the dominating mechanism of thermal quenching for Nd³⁺ and Er³⁺ ions is thermally stimulated non-radiative transitions (intersystem crossing) from the 5d states to lower-energy 4f levels, namely ²G(2)_9/2 and ²F(2)_7/2, respectively, whereas for the Tm³⁺ ion, thermally stimulated ionization of 5d electrons to the conduction band states is responsible for thermal quenching of 5d-4f luminescence. The energy gap between the lowest Tm³⁺ 5d level and the bottom of the KYF₄ conduction band has been estimated to be 0.66 eV.     

Fluorescence-quenching studies and temperature dependence of fluorescence quantum yield, decay time and intersystem crossing activation energy of TPB

Fluorescence quenching of 1, 1, 4, 4-tetraphenyl-1, 3-butadiene (TPB) by aniline has been carried out at room temperature (298 K) to understand the role of quenching mechanisms. The study has been carried out by both steady state (in different solvents) and by transient method (in cyclohexane). The Stern-Volmer plot has been found to be linear for all the solvents studied. The probability of quenching per encounter ‘p’ is determined in all the solvents and is found to be less than unity. It is found that, the activation energy E_a (E′_a) is greater than the activation energy of diffusion, E_d. The results obtained by the transient method infer that the thermally assisted intersystem crossing, a non-radiative deactivation process from S₁ to T₂ is responsible for observed decrease in quantum yield and lifetime. Hence, from both the methods it can be concluded that quenching mechanism is not solely due to the material diffusion, but there is also contribution from the activation energy.     

Polarity of the Medium and Quenching of Fluorescence of Caratenoids and Phthalimides

The relation for the dependence of the rate of radiationless energy conversion of the S ₁ state k _q on the polarity of the medium, obtained previously by the author, has been used to interpret the known literature data on the lifetime of the S ₁ state of solutions of some caratenoids and phthalimides. It has been shown that in alcohols and water (normal and deuterated ones) the fluorescence quenching of 4-amino-, 4-methylamino-, and 4-dimethylamino-N-methylphthalimides (4AMP, 4MAMP, and 4DMAMP) as well as of peridinine in alcohols is due to H-bond formation. It has been established that a twofold increase in the number of amine atoms of hydrogen on passing from 4MAMP to 4AMP, as well as deuteration of solvents in the case of 4DMAMP, is followed by a decrease in k _q by a factor of 1.6 and 1.75, respectively. The mechanism of quenching in complexes formed with solvent molecules by means of the H-bond is discussed. It has been concluded that the quenching of fluorescence of phthalimides in such complexes is mainly due to the intersystem crossing initiated by the oscillations of the protons or deuterons of the H-bonds.     

Fluorescence,Photophysical Behaviour and DFT Investigation of E,E-2,5-bis[2-(3-pyridyl)ethenyl]pyrazine (BPEP)

E,E-2,5-bis[2-(3-pyridyl)ethenyl]pyrazine (BPEP) has been prepared by aldol condensation between 2,5-dimethylpyrazine and pyridine-3-carboxaldehyde. It is characterized by IR, ¹H NMR, and ¹³C NMR. The electronic absorption and emission properties of BPEP were studied in different solvents. BPEP displays a slight solvatochromic effect of the absorption and emission spectrum, indicating a small change in dipole moment of BPEP upon excitation. The dye solutions (1 × 10^?4 M) in CHCl₃, EtOH and dioxane give laser emission in blue region upon excitation by a 337.1 nm nitrogen pulse (λ = 337 nm). The tuning range, gain coefficient (α) and emission cross – section (σ_e) have been determined. Ground and excited states electronic geometric optimizations were performed using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), respectively. A DFT natural bond analysis complemented the ICT. The simulated maximum absorption and emission wavelengths are in line the observed ones in trend, and are proportionally red-shifted with the increase of the solvent polarity. The stability, hardness and electrophilicity of BPEP in different solvents were correlated with the polarity of the elected solvents. BPEP dye displays fluorescence quenching by colloidal silver nanoparticles (AgNPs). The fluorescence data reveal that radiative and non-radiative energy transfer play a major role in the fluorescence quenching mechanism.     

Preparation and Photophysics of 2-(1-Pyrenyl)acrylic Acid and Its Methyl and 2′,2′,6′,6′-Tetramethyl-4′-Piperidyl Esters

Novel probes represented connection of pyrene as chromophore and sterically hindered amine stabilizers (HAS) in the form of esters of 2-(1-pyrenyl)acrylic acid were synthesized. HAS was in the form of parent amine (PAP) as well as stable nitroxyl radical form (PAP-NO^.). Photophysics of these probes were compared with their precursor as 2-(1-pyrenyl)acrylic acid (PAA) and its methyl ester (PAM). The fluorescence spectrum of PAA strongly depends on the acidity of the solution. The spectrum in neutral methanol indicates that it originates from the anionic form –COO⁻. Changes of acidity or basicity of methanol solution resulted in the changes of shape, position as well as the intensity of fluorescence band. This is due to the presence of protolytic equilibria, either in the ground state or in the singlet excited state, leading to the formation of molecular form –COOH and the cationic form –COOH₂⁺. The ester analogues did not show any changes in various pH conditions. Fluorescence of all probes depends on the polarity of solvents and the presence of oxygen. Intermolecular quenching was studied with external quenchers TEMPO and oxygen and the data were compared with the intramolecular quenching using 1′-oxo-2′,2′,6′,6′-tetramethyl-4′-piperidinyl-2-(1-pyrenyl)acrylate (PAP-NO^.).     

Investigation of the fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by certain substituted uracils

The fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by a series of uracils has been studied in water and acetonitrile solvents using steady-state and time-resolved fluorescence techniques. The steady-state fluorescence quenching technique has been performed in three different pHs (i.e. 4, 8 and 12). The bimolecular quenching rate constant (k_q) increases with increase in pH of uracils. In acidic pH, a pure hydrogen atom abstraction is proposed as the quenching mechanism. This is supported by a pronounced solvent deuterium isotope effect. Electron transfer from the anionic form of uracil to the excited state of DBO is proposed as a mechanism for quenching in basic pH on the basis of highly exergonic thermodynamics obtained from the Rehm-Weller equation. The variation of k_q is explained on the basis of the electronic effect of substitution in uracils as well.     

Fluorescence quenching of fluorescein by Merocyanine 540 in liposomes

The fluorescence quenching of fluorescein (FL) by merociyanine 540 (MC540) was examined in L-egg lecithin phosphatidycholine (PC) liposomes using spectroscopic methods. The type of quenching mechanism (dynamic or static) was evaluated using the Stern-Volmer plots. Findings were also supported by the temperature studies and florescence decay measurements. The Stern-Volmer equation was utilized to calculate bimolecular quenching constants (K_q). Furthermore, the bimolecular quenching constant of the quencher in the liposomes (K_SV), partition coefficient (K_p), binding constant (K), and corresponding thermodynamic parameters ΔH, ΔS, and ΔG were calculated. The quenching property was also used in determining quantitatively (K_p) the partition coefficient of Merociyanini 540 in PC liposome.The obtained data indicated that static quenching occurred in the system and the K_SV values decreased with increasing lipid concentration. In addition, thermodynamic analysis suggested that van der Waals interactions and hydrogen bonding were the main acting forces between fluorescein and merociyanine 540 molecules in the medium.     

A quenching fluoroimmunoassay for analysis of the pesticide propazine in an apolar organic solvent, reverse micelles of AOT inn-octane: Effect of the micellar matrix and labeled antigen structure

A simple way of directly observing antigen-antibody binding in a reverse micellar system,n-octane containing reverse micelles of aerosol OT (AOT), using the hydrophobic pesticide propazine as antigen, is described. We observed two processes during fluorescein-labeled propazine (FP)-antibody (Ab) interaction in reverse micelles: (1) quenching of the fluorescence of FP after mixing of Ab and FP (due immune complex formation) and (2) restoration of FP fluorescence after addition of excess propazine to the immune complex formed. We found that the quenching efficiency depends on both the properties of the reverse micellar system (surfactant concentration, hydration degreeW ₀ = [water]/[surfactant]) and the structure of the labeled antigen. A quenching fluoroimmunoassay of propazine both in apolar organic solvents and in water is developed. The method is homogeneous. The quenching time is 10–30 min, and the detection limit of propazine is 100 nM (20 Μg/L) in organic solvent and 10nM (2 Μg/L) in water. Propazine can be added to the reverse micellar system when dissolved in AOT/octane, or in an octane/chloroform mixture, or in chloroform. This makes possible the use of the analysis directly for pesticide extracts in nonpolar organic solvents.     

Photoinduced interaction between MPA capped CdTe QDs and certain anthraquinone dyes

Photoinduced interaction of mercapto propionic acid (MPA) capped CdTe quantum dots (QDs) with certain anthraquinone dyes namely alizarin, alizarin red S, acid blue 129 and uniblue has been studied by steady state and time resolved fluorescence measurements. Addition of anthraquinone dyes to CdTe QDs results in the reduction of electron hole recombination has been observed (i.e., fluorescence quenching). The Stern-Volmer constant (K_SV), quenching rate constant (k_q) and association constants (K) were obtained from fluorescence quenching data. The interaction of anthraquinone dyes with QDs occurs through static quenching was confirmed by unaltered fluorescence lifetime. The occurrence of electron transfer quenching mechanism has been proved by the negative free energy change (ΔG_et) obtained as per the Rehm-Weller equation.     

Fluorescence quenching of newly synthesized biologically active coumarin derivative by aniline in binary solvent mixtures

The fluorescence quenching of newly synthesized coumarin (chromen-2-one) derivative, 4-(5-methyl-3-furan-2-yl-benzofuran-2-yl)-7-methyl-chromen-2-one (MFBMC) by aniline in different solvent mixtures of benzene and acetonitrile was determined at room temperature (296 K) by steady-state fluorescence measurements. The quenching is found to be appreciable and positive deviation from linearity was observed in the Stern-Volmer (S-V) plots in all the solvent mixtures. This could be explained by static and dynamic quenching models. The positive deviation in the S-V plot is interpreted in terms of ground-state complex formation model and sphere of action static quenching model. Various rate parameters for the fluorescence quenching process have been determined by using the modified Stern-Volmer equation. The sphere of action static quenching model agrees very well with experimental results. The dependence of Stern-Volmer constant K_SV, on dielectric constant ε of the solvent mixture suggests that the fluorescence quenching is diffusion-limited. Further with the use of finite sink approximation model, it is concluded that these bimolecular quenching reactions are diffusion-limited. Using lifetime (τ_o) data, the distance parameter R′ and mutual diffusion coefficient D are estimated independently.     

Synthesis, Characterization, and Luminescence Spectroscopic Accessibility Studies of tris(2,2′-Bipyridine)Ruthenium(II)-Labeled Inorganic-Organic Hybrid Polymers

The modified tris(2,2-bipyridine)ruthenium(II) complex 2 was anchored via a sol-gel process to different polysiloxane matrices to give a series of novel inorganic–organic hybrid polymers. One of the bipyridine ligands of 2 was provided with a long-chain spacer carrying a triethoxysilyl function (T group) at the end, which enables almost free mobility of the transition metal center. The polymers were swollen in several organic solvents of different polarity to investigate the luminescence behavior in the presence of quencher molecules. The luminescence of 2 was quenched using anthracene and atmospheric oxygen in appropriate concentrations of 5 · 10^–4 to 5 · 10^–3 and 3 · 10^–3 M, respectively. The luminescence behavior of 2 was determined by steady-state and time-resolved luminescence experiments. Translational mobilities of molecular species dissolved in the liquid phase were investigated by the kinetics of luminescence quenching after laser excitation. Both the translational mobility of anthracene and atmospheric oxygen, specified with the rate constant k₂ and the percentage of accessible luminescent centers were determined. Translational mobilities and the accessibility for anthracene and atmospheric oxygen in hybrid materials are significantly higher than in conventional Q type polysiloxanes.     

Role of charge-transfer complexes in oxygen quenching of excited states of anthracene derivatives in the gas phase

Oxygen quenching of excited triplet and singlet states of gas-phase anthracene and its derivatives that have similar energies of the lower triplet levels but widely different oxidation potentials (0.44 < E_ox < 1.89 V) was studied. Quenching rate constants for singlet (k_S^O2) and triplet (k_T^O2) states in addition to the fraction of oxygen-quenched singlet and triplet states q_{S 1}(T₁^O2 were determined from the decay rates, fluorescence intensities, and delayed fluorescence as functions of oxygen pressure. It was found that k_S^O2 values vary from 2·10⁴ (9,10-dicyanoanthracene) to 1.2·10⁷ sec⁻¹·torr⁻¹ (anthracene, 9-methylanthracene, 2-aminoanthracene) and k_S^O2 values from 5·10² to 1·10⁵ sec⁻¹·torr⁻¹. The k_S^O2 values for anthracene, 9-methylanthracene, and 2-aminoanthracene, which have fast rates of interconversion from S₁ to T₁, are close to the rate constants for gas-kinetic collisions and are independent of the oxidation potentials (E_ox). The quenching rate constants k_S^O2 for the other anthracene derivatives and k_T^O2 for all studied compounds decrease with increasing free energy of electron transfer ΔG_ET, which indicates the important role of charge-transfer interactions in the oxygen quenching of singlet S_1- and triplet T₁ states. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 36–42, January–February, 2008.     

Fluorescence Quenching of 2,2″-dimethyl-p-terphenyl by Carbon Tetrachloride in Binary Mixtures

The fluorescence quenching of 2,2″-dimethyl-p-terphenyl (DMT) by carbon tetrachloride (CCl₄) was investigated in different solvent mixtures of benzene and acetonitrile at room temperature (300 K). A positive deviation from linearity was observed in the Stern-Volmer plots for all the solvent mixtures. This could be explained satisfactorily by static and dynamic quenching models. The nonlinearities in the S-V plots are interpreted in terms of ground state complex model and the sphere of action static quenching model. The results suggest that positive deviations in the S-V plot are due to the presence of both static and dynamic quenching processes. To explain that bimolecular reactions are diffusion limited, we have used finite sink approximation model. Various rate parameters for the quenching process have been determined by static and dynamic quenching models. The dynamic quenching constant depends on the solvent polarity and indicates that quenching reaction is diffusion limited.     

Depletion of singlet and triplet states of 1-amino-5, 6, 7, 8-tetrahydronaphthalene due to external heavy-atom perturbation

Summary Quenching of luminescence of 1-amino-5, 6, 7, 8-tetrahydronaphthalene (ATHN) in nonpolar and polar solvents at 300 K and 77 K by the chloroalkanes carbon tetrachloride (CCl₄), methyl chloroform (CH₃CCl₃), chloroform (CHCl₃) and methylene chloride (CH₂Cl₂) is reported. Different photophysical parameters at 77 K of unperturbed and perturbed fluorescer ATHN in ternary solutions are determined. The bimolecular dynamic fluorescence quenching rate constant (K _q) increases with the electron affinity (EA) of the quenchers and a linear correlation exists between lnK _q and EA. The quenching depends on polarity of solvents. The quenching is ascribed to contact CT exciplex formed between chloroalkanes and excited singlet ATHN.

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Riassunto Si riporta lo spegnimento di luminescenza dell' l-amino-5, 6, 7, 8-tetraidronaftalene (ATHN) in solventi non polari e polari a 300 K e 77 K mediante i cloroalcani tetracloruro di metilene (CH₂Cl₂). Si determinano diversi parametri fotofisici a 77 K di ATHN fluorescente perturbato e non perturbato in soluzioni ternarie. La constante (K _q) del valore di smorzamento di fluorescenza dinamico bimolecolare aumenta con l'affinità elettronica (EA) degli spegnitori ed esiste una correlazione lineare tra lnK _q ed EA. Lo spegnimento dipende dalla polarità dei solventi. Lo spegnimento è attribuito all'exciplex CT di contatto formato tra cloroalcani e ATHN a singoletti eccitati.

     

Oxygen fluorescence quenching studies with single tryptophan-containing proteins

The work of Lakowicz and Weber [Biochemistry 12, 4161 (1973)] demonstrated that molecular oxygen is a powerful quencher of tryptophan fluorescence in proteins. Here we report studies of the oxygen quenching of several proteins that have a single, internal tryptophan residue. Among these are apoazurin (Pseudomonas aeruginosa), asparaginase (Escherichia coli), ribonuclease T₁ (Aspergillus oryzae), and cod parvalbumin. Both fluorescence intensity and phase lifetime quenching data are reported. By comparison of these data we find that there is a significant degree of apparent static quenching in these proteins. The dynamic quenching rate constants,k _q, that we find are low compared to those for tryptophan residues in other proteins. For example, for apoazurin we find an apparentk _q of 0.59×10⁹ M ^–1 s^–1 at 25°C. This value is the lowest that has been reported for the oxygen quenching of tryptophan fluorescence.     

Fluorescence quenching of 2,2″ dimethyl-p-terphenyl by carbon tetrachloride in different solvents and temperatures

The fluorescence quenching of 2,2″-dimethyl-p-terphenyl (DMT) by carbon tetrachloride by steady state in different solvents, and by transient method in benzene has been carried out at room temperature. The Stern-Volmer (SV) plot has been found to be non-linear with a positive deviation for all the solvents studied. In order to interpret these results we have invoked the ground state complex and sphere of action static quenching models. Using these models various rate parameters have been determined. The magnitudes of these parameters imply that sphere of action static quenching model agrees well with the experimental results. Hence the positive deviation in the SV plots is attributed to the static and dynamic quenching. Further, from the studies of temperature dependence of rate parameters and lifetime measurements, it could be explained that the positive deviation is due to the presence of a small static quenching component in the overall dynamic quenching. With the use of finite sink approximation model, it was possible to check whether these bimolecular reactions as diffusion limited and to estimate independently distance parameter R′ and mutual diffusion coefficient D. Finally an effort has been made to correlate the values of R′ and D with the values of the encounter distance R and the mutual diffusion coefficient D determined using the Edward's empirical relation and Stokes-Einstein relation.