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.

     

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.     

Simultaneous presence of static and dynamic component in the fluorescence quenching of Bis-MSB by CCl4 and aniline

The fluorescence quenching of 1, 4-bis[2-(2-methylphenyl)ethenyl]-benzene (Bis-MSB) in toluene has been studied with carbon tetrachloride (CCl₄) and aniline by steady-state and transient methods. A positive deviation was observed in the Stern-Volmer (S-V) plot for both the quenchers. This indicates the presence of either static or transient quenching component in the overall dynamic quenching. The experimental data are analysed by sphere of action static quenching model. The value of radius of sphere of action determined from this model is greater than the sum of the radii of the Bis-MSB and respective quenchers. 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. This fact suggests the simultaneous presence of static and dynamic component in the fluorescence quenching Bis-MSB by CCl₄ and aniline.     

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.     

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.     

Static and dynamic quenching of biologically active coumarin derivative by aniline in benzene-acetonitrile mixtures

The fluorescence quenching of coumarin derivative, 4-(5-chloro-3-furan-2-yl-benzofuran-2-yl)-6-methyl-2H-chromen-2-one (ClFBMC), in the presence of aniline in different proportion of benzene-acetonitrile mixture was studied by means of steady-state measurement (296 K). The quenching process was characterized by Stern-Volmer (S-V) plots, which display positive (upward) deviation. The positive deviation from linearity suggests that the quenching is due to the simultaneous presence of dynamic and static quenching, which is interpreted in terms of the ground-state complex formation and the sphere of action static quenching model. The sphere of action static quenching model agrees very well with experimental results. Further with the use of finite sink approximation model, it is concluded that the bimolecular quenching reactions are diffusion-limited. Various rate parameters for the fluorescence quenching process have been determined. The value of quenching constant k_q increases with increase in dielectric constant of the mixed solvent, suggesting the charge transfer character of the excited complex.     

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.     

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.     

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.     

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.     

Spectroscopic studies of 7, 8-dihydroxy-4-methylcoumarin and its interaction with bovine serum albumin

The absorption and fluorescence spectra of 7, 8-dihydroxy-4-methylcoumarin (DHMC) in ethanol-water (1:9 v/v) solution at varying pH values were investigated . The interaction between DHMC and bovine serum albumin (BSA) was investigated by fluorescence, FT-IR, and circular dichroism (CD) spectroscopy. The Stern-Volmer quenching constant (K_SV), the quenching rate constant of the bimolecular reaction (K_q), the binding constant, and number of binding sites (n) of DHMC with BSA were evaluated. The results showed that DHMC quenches the fluorescence intensity of BSA through a static quenching process. Positive value of entropy change (ΔS) and negative value of enthalpy change (ΔH) of the BSA-DHMC interaction were obtained according to the van't Hoff equation. The interaction between DHMC and BSA was driven mainly by hydrophobic forces. The binding process was spontaneous and exothermic. The binding distance between the tryptophan residue in BSA and the DHMC was found to be about 2.6 nm based on the Förster theory of non-radiation energy transfer.     

Combined Quenching Mechanism of Anthracene Fluorescence by Cetylpyridinium Chloride in Sodium Dodecyl Sulfate Micelles

The Stern-Volmer quenching constant (K_SV) for quenching of anthracene fluorescence in sodium dodecyl sulfate (SDS) micelles by pyridinium chloride has been reported previously to be 520 M^?1 based on steady state fluorescence measurements. However, such measurements cannot distinguish static versus dynamic contributions to the overall quenching. In the work reported here, the quenching dynamics of anthracene in SDS micelles by cetylpyridinium chloride (CPC), an analogue of pyridinium chloride, were investigated using both steady state and time resolved fluorescence quenching. Concurrent measurement of the decrease in fluorescence intensity and lifetime of anthracene provide a quantitative evaluation of collision induced (i.e. dynamic) versus complex formation (i.e. static) quenching of the anthracene fluorophore. The results reveal that a combined quenching mechanism is operative with approximately equal constants of 249?±?6 M^?1 and 225?±?12 M^?1 for dynamic and static quenching, respectively.     

Interactions between imazethapyr and bovine serum albumin: Spectrofluorimetric study

The interaction between imazethapyr (IMA) and bovine serum albumin (BSA) was investigated by fluorescence spectroscopy. The Stern–Volmer quenching constant (K_SV) at three temperatures was evaluated in order to determine the quenching mechanism. The dependence of fluorescence quenching on viscosity was also evaluated for this purpose. The results showed that IMA quenches the fluorescence intensity of BSA through a static quenching process. The values of the binding constant for the formed BSA–IMA complex and the number of binding sites were found to be 1.51×10⁵ M^?1 and 0.77, respectively, at room temperature. Based on the calculated thermodynamic parameters, the forces that dominate the binding process are hydrogen bonds and van der Waals forces, and the binding process is spontaneous and exothermic. The quenching of protein fluorescence by iodide ion was used to probe the accessibility of tryptophan residues in BSA and the change in accessibility induced by the presence of IMA. According to the obtained results, the BSA–IMA complex is formed in the site where the Trp-134 is located, causing it to become less exposed to the solvent.     

Fluorescence Quenching of 2-Amino-9-Hydroxy Fluorene by Chloromethanes

Fluorescence quenching of 2-amino-9-hydroxyfluorene by CCl₄, CHCl₃, and CH₂Cl₂ was investigated in solvents of different polarity. The results reveal that the mechanism of quenching is purely dynamic (complex formed in excited state). The bimolecular quenching-rate constants (k_q) correlate well with electron affinity of the quenchers. They are also dependent on the polarity of the solvents, confirming the formation of charge-transfer nonemissive exciplex.     

Investigation of three flavonoids binding to bovine serum albumin using molecular fluorescence technique

The three flavonoids including naringenin, hesperetin and apigenin binding to bovine serum albumin (BSA) at pH 7.4 was studied by fluorescence quenching, synchronous fluorescence and UV–vis absorption spectroscopic techniques. The results obtained revealed that naringenin, hesperetin and apigenin strongly quenched the intrinsic fluorescence of BSA. The Stern–Volmer curves suggested that these quenching processes were all static quenching processes. At 291 K, the value and the order of the binding constant were K_{A (naringenin)}=4.08×10⁴<K_{A (hesperetin)}=5.40×10⁴≈K_{A (apigenin)}=5.32×10⁴ L mol^?1. The main binding force between the flavonoid and BSA was hydrophobic and electrostatic force. According to the Förster theory of non-radiation energy transfer, the binding distances (r₀) were obtained as 3.36, 3.47 and 3.30 nm for naringenin–BSA, hesperetin–BSA and apigenin–BSA, respectively. The effect of some common ions such as Fe³⁺, Cu²⁺, Mg²⁺, Mn²⁺, Zn²⁺ and Ca²⁺ on the binding was also studied in detail. The competition binding was also performed. The apparent binding constant (K′_A) obtained suggested that one flavonoid had an obvious effect on the binding of another flavonoid to protein when they coexisted in BSA solution.     

Analysis of fluorescence quenching of pyronin B and pyronin Y by molecular oxygen in aqueous solution

The fluorescence quenching of pyronin B and pyronin Y molecules by molecular oxygen in aqueous solution was studied by using steady-state and time-resolved fluorescence and UV-Vis absorption spectroscopy techniques. In order to understand the quenching mechanism, fluorescence decays, absorption and fluorescence spectra of the probes were recorded as a function of the oxygen concentration and temperature. The quenching was found to be appreciable and shows positive deviation in the Stern-Volmer representation obtained from the fluorescence intensity ratio. Fluorescence quenching constants (k_q) were calculated from the τ_o/τ vs. [Q] plots having linear correlation and compared with calculated diffusion-controlled rate constants (k_diff) values. Experimental results were in good agreement with the simultaneous dynamic and static quenching model.     

Preferential Solvation of 1,4-Dimethoxy-2,3-Dimethyl-9,10-Anthraquinone-A Spectrophotometric and Fluorometric Study

Electronic absorption and fluorescence emission spectra of DMDMAQ (1,4-dimethoxy-2,3-dimethyl-9,10-anthraquinone) have been studied as a function of solvent composition in some binary mixtures and in different neat solvents. The binary mixtures consist CCl₄ (Carbon tetrachloride)-DMSO (Dimethylsulfoxide), EtOH (Ethanol)-DMSO, and CCl₄-EtOH combination of single solvents. The wavelength maxima of the absorption band for DMDMAQ are quite solvent sensitive in aprotic solvents. But, in protic solvent, there is no marked shift in absorption and emission maximum which shows the absence of specific interaction. Excited state shows increasing shift with increasing solvent polarity compared to ground state. The ratio of dipole moment in the excited state to that in the ground state was calculated. Different criteria were considered to analyse preferential solvation characteristics in different binary mixtures, viz., local mole fraction (), solvation index (δ_S2) and exchange constant (K₁₂).     

Development of muon polarization preserved scintillators

We measured the residual μ⁺ polarizations in various liquid scintillators to search for an ideal material for an active muon stopper in which the muon spin polarization can be preserved and at the same time their energy loss and tracks can be measured by scintillation lights from the stopper material. We found the residual polarizations of mineral‐oil base liquid scintillators were \sim 4 times larger than that of a plastic scintillator. Further increase of the residual polarization was observed with a mixture of CCl₄. This revised version was published online in August 2006 with corrections to the Cover Date.     

Interaction of ZnS nanoparticles with flavins and glucose oxidase: A fluorimetric investigation

Interactions of luminescence, water soluble ZnS nanoparticles (NPs) with flavins and glucose oxidase have been thoroughly investigated through optical spectroscopy. The photoluminescence of ZnS nanoparticles was quenched severely (～60%) by riboflavin while other flavins such as flavin mononucleotide (FMN) and flavin adenine dinucleotide (FAD) show quenching to different extents under analogous conditions. However, interestingly no effect in luminescence intensity of ZnS NPs was observed with protein bound flavins such as in glucose oxidase. Fluorescence lifetime measurement confirmed the quenching to be static in nature. Scavenging of photo-generated electron of ZnS nanoparticles by the flavin molecules may be attributed to the decrease in luminescence intensity. Quenching of ZnS nanoparticles with flavins follows the linear Stern–Volmer plot. The Stern–Volmer constants decreased in the following order: K_S?V (Riboflavin)> K_S?V (FAD)> K_S?V (FMN). This interaction study could generate useful protocol for the fluorimetric determination of riboflavin (vitamin B₂) content and also riboflavin status in biological systems.