Stern-Volmer Kinetics Research Articles

Ultrasensitive detection of Ag+ and Ce3+ ions using highly fluorescent carboxyl-functionalized carbon nitride nanoparticles

The fluorescence quenching of carboxyl-rich g-C3N4 nanoparticles was found to be selective to Ag+ and Ce3+ with a limit of detection as low as 30 pM for Ag+ ions. A solid-state thermal polycondensation reaction was used to produce g-C3N4 nanoparticles with distinct green fluorescence and high water solubility. Dynamic light scattering indicated an average nanoparticle size of 95 nm. The photoluminescence absorption and emission maxima were centered at 405 nm and 540 nm respectively which resulted in a large Stokes shift. Among different metal ion species, the carboxyl-rich g-C3N4 nanoparticles were selective to Ag+ and Ce3+ ions, as indicated by strong fluorescence quenching and a change in the fluorescence lifetime. The PL sensing of heavy metal ions followed modified Stern–Volmer kinetics, and CNNPs in the presence of Ag+/Ce3+ resulted in a higher value of K app (8.9 × 104 M−1) indicating a more efficient quenching process and stronger interaction between CNNP and mixed ions. Sensing was also demonstrated using commercial filter paper functionalized with g-C3N4 nanoparticles, enabling practical on-site applications.

Photophysics of a Monoannulated Indigo: Intra- and Intermolecular Charge Transfer.

In the present work, the photoinduced charge-transfer (CT) behavior of 7-phenyl-6H-pyrido[1,2-a:3,4-b']diindole-6,13(12H)-dione (HCB) as a function of solvent polarity is reported by UV-vis absorption, steady-state and time-resolved fluorescence, and quantum chemical calculations. Calculated excited state energies of HCB at the B3PW91/6-31+G* level in vacuo and in solvents fulfill the energy requirements for singlet fission, which is the most promising path for the generation of highly efficient solar cells. The calculated potential energy curve for the compound reveals that the keto form is the predominant form in the ground state. Large bathochromic shifts in fluorescence with decreasing trends of quantum yield and lifetime indicate the occurrence of intramolecular CT from the indole bicycle to the indolinone moiety of HCB in highly polar solvents. The observed quenching of HCB fluorescence in different solvents without altering the spectral shape upon addition of a donor, triethylamine, is attributed to intermolecular CT, and it was examined in terms of the Stern-Volmer kinetics. The thermodynamics of photoinduced CT processes in HCB was analyzed using the measured photophysical data and cyclic voltammetric redox potentials via the Rehm-Weller equation. Analyses with the semiclassical Marcus theory suggest that both the CT processes fall under the Marcus normal region.

Study of Photophysical Properties of Thiol-capped CdS Quantum Dots Doped with Gold Nanoparticles.

In this study, CdS quantum dots (QDs) capped with benzyl mercaptan (thiol) were prepared by microwave irradiation technique. The shape, size, morphology, and spectral properties of thiol-capped CdS QDs were characterized with transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV-vis absorption, and photoluminescence (PL) spectrometry. The photophysical properties of synthesized thiol-capped CdS QDs in the presence of different amounts of gold nanoparticles (AuNPs) have been investigated, exhibiting strong PL quenching. The amount of fluorescence quenching was found to be dependent on the concentration of metal nanoparticles. A Stern-Volmer kinetics model was used to analyze the observed quenching mechanism as a function of the quencher (AuNPs) concentration. The Stern-Volmer plot along with the absorption spectra of thiol-capped CdS QDs in the absence and presence of AuNPs suggest the dynamic (collision) nature of quenching and rule out the possibility of static quenching. The energy transfers from QDs to Au NPs, and hence the quenching of QDs emissions provides new insight into designing novel optical-based materials and the development of FRET-based bionanosensors and phototherapeutic applications.

Enhanced luminescence sensing performance and increased intrachain order in blended films of P3HT and cellulose nanocrystals

Blended films comprising poly(butyl acrylate) (PBA)-grafted cellulose nanocrystals (CNCs) and poly(3-hexylthiophene) (P3HT), exhibited more intense photoluminescence (PL) and longer PL emission lifetimes compared to pristine P3HT films. Optical absorption and photoluminescence spectra indicated reduced torsional disorder i.e. enhanced backbone planarity in the P3HT@CNC blended composites compared to the bare P3HT. Such molecule-level geometrical modification resulted in both smaller interchain and higher intrachain exciton bandwidth in the blended composites compared to the bare P3HT, because of reduced interchain interactions and enhanced intrachain order. These results indicate a potential switch of the aggregation behavior from dominant H-aggregates to J-aggregates, supported by Raman spectroscopy. The reorganization of micromolecular structure and concomitant macroscopic aggregation of the conjugated polymer chains resulted in a longer conjugation length for the P3HT@CNC blended composites compared to the bare P3HT. Additionally, this nanoscale morphological change produced a reduction in the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gap of the blends, evidenced from optical absorption spectra. Classical molecular dynamics simulation studies predicted the probability of enhanced planarity in the polymer backbone following interactions with CNC surfaces. Theoretical results from density functional theory calculations corroborate the experimentally observed reduction of optical bandgap in the blends compared to bare P3HT. The blended composite outperformed the bare P3HT in nitro-group PL sensing tests with a pronounced difference in the reaction kinetics. While the PL quenching dynamics for bare P3HT followed Stern–Volmer kinetics, the P3HT@CNC blended composite exhibited a drastic deviation from the same. This work shows the potential of a functionalized rod-like biopolymer in tuning the optoelectronic properties of a technologically important polymeric organic semiconductor through control of the nanoscale morphology.

Novel metallophthalocyanines with bulky 4-[3,4-bis(benzyloxy)benzylidene]aminophenoxy substituents

Novel metallophthalocyanines substituted with four peripheral 4-[3,4-bis(benzyloxy)benzylidene]aminophenoxy groups were prepared by Schiff base condensation of 4-aminophenoxy-substituted phthalocyanines with 3,4-bis(benzyloxy)benzaldehyde. The structures were elucidated with elemental analysis, Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectrometry, and matrix assisted laser desorption ionization-time of flight spectrometry along with Ultraviolet–Visible spectrophotometry. In the studied concentration range of 1–10 × 10−6 M, no appreciable aggregation of the new species was detected. In tetrahydrofuran, the fluorescent quantum yield ΦF value of the zinc phthalocyanine was lower than the unsubstituted ZnPc (ΦF = 0.25) due to the peripheral [3,4-bis(benzyloxy)benzylidene]aminophenoxy substituents which surely caused fluorescence quenching. The zinc phthalocyanine showed fluorescent quenching by the addition of 1,4-benzoquinone in tetrahydrofuran with obedience to Stern–Volmer kinetics.

A molecularly imprinted polymer placed on the surface of graphene oxide and doped with Mn(II)-doped ZnS quantum dots for selective fluorometric determination of acrylamide.

A polymer imprinted with acrylamide (AM-MIP) was synthesized on the surface of graphene oxide by surface polymerization of propionamide (serving as a dummy template), methacrylic acid (as the functional monomer) and ethylene glycol dimethacrylate (the cross-linker). ZnS quantum dots (QDs) doped with Mn(II) ions were added to the AM-MIP to act as fluorescence source. The AM-MIP was characterized by infrared spectroscopy, scanning electron microscopy and X-ray powder diffraction, suggesting that the imprinted layer was successfully grafted onto graphene oxide. The fluorescence of the doped QDs is quenched when loading the AM-MIP with acrylamide (AM), and the quenching effect is much stronger than the non-imprinted polymer (AM-NIP). Quenching follows Stern-Volmer kinetics. The combination of imprinting and fluorometric detection offer AM-IIP capability to accumulate trace AM before direct determination, omitting desorption and separation or other methods. The excitation and emission spectra of AM-MIP peak at 325nm and 601nm, respectively. Under optimal conditions, fluorescence drops linearly in the 0.5-60μmol·L-1 acrylamide concentration range, and the detection limit is 0.17μmol·L-1. The method has been applied to the determination of AM in spiked water samples and gave recoveries in the range from 100.2 to 104.5%, with relative standard deviations in the 1.9 to 3.9% range. In our perception, the AM-MIP presented here is a promising fluorescent probe for the detection of trace acrylamide in food. Graphical abstract Schematic of the preparation of graphene oxide coated with a molecularly imprinted polymer doped with Mn(II)-doped ZnS quantum dots. Propionamide serves as a dummy template. Acrylamide acts as a quencher of fluorescence, and this effect is used for its selective fluorometric determination.

Interaction of two flavonols with fat mass and obesity-associated protein investigated by fluorescence quenching and molecular docking

The binding of two flavonols with fat mass and obesity-associated protein (FTO) was studied using fluorescence spectroscopy, Stern-Volmer kinetics, UV-Vis absorption, and molecular docking. The quenching of FTO fluorescence was determined to be static with binding constants on the order of 104 M−1. The interaction was studied over three temperatures, and the binding was found to be exothermic with a positive change in entropy. Thermodynamic analysis and molecular modeling suggest that hydrophobic interaction and hydrogen bonding interaction are the main binding force in stabilizing the flavonol–FTO complex.

Synthesis and time resolved infrared analysis of photochemical oxiranyl carbene and diphenyl ketene precursors

Synthesis of a nonnitrogenous phenanthrene-based precursor of oxiranyl carbene yielded a photochemical source for diphenyl ketene after an in situ intramolecular rearrangement. The initial carbene precursor targeted rearranged from a putative spiro-oxiranyl intermediate to a cyclobutanone. Photolysis of the phenanthrene–cyclobutanone generated an infrared signal centered at 2100cm−1 consistent with diphenyl ketene formation. Time-resolved infrared spectroscopy followed the reaction progress and measured bimolecular rate constants (kobs=9.1×106M−1s−1; butyl amine) consistent with diphenyl ketene formation. Quenching experiments combined with Stern–Volmer kinetics suggests a radical pathway is likely involved in the formation of diphenyl ketene from the phenanthrene-based precursor. The generality of the rearrangement is also discussed.

Interaction of Small Zinc Complexes with Globular Proteins and Free Tryptophan

A series of eight water soluble anionic, cationic, and neutral zinc(II) complexes were synthesized and characterized. The interaction of these complexes with bovine serum albumin (BSA), human serum albumin (HSA), lysozyme, and free tryptophan (Trp) was investigated using steady-state fluorescence spectroscopy. Static and dynamic fluorescence quenching analysis based on Stern-Volmer kinetics was conducted, and the decrease in fluorescence intensity of the Trp residue(s) can be ascribed predominantly to static quenching that occurs when the Zn complex binds to the protein and forms a nonfluorescent complex. The role played by the nature of the ligand, the metal, and complex charge in quenching Trp fluorescence was investigated. The binding association constants (Ka) ranged from 104to 1010 M−1and indicate that complexes with planar aromatic features have the strongest affinity for globular proteins and free Trp. Complexes with nonaromatic features failed to interact with these proteins at or in the vicinity of the Trp residues. These interactions were studied over a range of temperatures, and binding was found to weaken with the increase in temperature and was exothermic with a negative change in entropy. The thermodynamic parameters suggest that binding of Zn complexes to the proteins is a highly spontaneous and favorable process.

Exploring the mechanism of fluorescence quenching in two biologically active boronic acid derivatives using Stern-Volmer kinetics

The fluorescence quenching of 5-chloro-2-methoxyphenylboronic acid (5CMPBA) and 4-fluoro-2-methoxyphenyl boronic acid (4FMPBA) has been studied at room temperature by steady state fluorescence measurements. Aniline is used as quencher. Emission spectra are corrected for inner filter effect. The positive deviation observed in Stern-Volmer (S-V) plot is analyzed using different quenching models. Various quenching parameters like Stern-Volmer constant (KSV), quenching rate parameter (kq), volume constant (V), and kinetic distance (r) are estimated using extended S-V equations. The calculated values of quenching parameters suggest that static quenching mechanism is active in the studied system provided that the reactions are diffusion limited. Finite sink approximation model is invoked in order to check whether reactions are diffusion limited.

Static quenching of tryptophan fluorescence in proteins by a dioxomolybdenum(VI) thiolate complex

Abstract The binding of cis-dioxobis(dithiocarbamato) molybdenum(VI) with the proteins bovine serum albumin, human serum albumin, lysozyme, and free tryptophan was studied using fluorescence spectroscopy and Stern–Volmer kinetics. The quenching of tryptophan fluorescence was determined to be static with binding constants on the order of 104–105 M−1, and with a binding site number of one. The interaction was studied over a range of temperatures, and the binding was found to be exothermic with a negative change in entropy. Quantum chemical calculations were also conducted to identify optimal spatial contacts and the resulting energetic contributions between the complex and free tryptophan.

Fluorescence quenching studies on the interaction of a novel deepened cavitand towards some transition metal ions

A novel ‘three-level’ deepened cavitand featuring a significantly sizable portal has been synthesized and its interaction with some transition metal ions has been investigated in THF/H2O binary solvent using fluorescence quenching technique. The results suggest that among the used transition metal ions including Ag+, Cd2+, Cu2+, Fe3+, Cr3+, Hg2+, La3+, Mn2+, Ni2+, Zn2+ and Co2+, only Fe3+ and Cu2+ show good quenching ability. In order to interpret the quenching mechanism, the Stern–Volmer kinetics, and the presence of both the dynamic and static quenching have been discussed. It was found that the simultaneous presence of the sphere-of-action static quenching and dynamic quenching model agrees very well with the experimental results. The limits of detection for Fe3+ and Cu2+ were found to be 2.1×10−6molL−1 (3σ) and 3.6×10−6molL−1 (3σ), respectively. Cations with potential interference, such as K+, Na+, Mg2+, Ca2+, Co2+, La3+ and Mn2+ do not have significant effects on the determinations of Fe3+ and Cu2+. This cavitand can be potentially applied as optical sensor for the detection of Fe3+ and Cu2+.

Static and Dynamic Quenching of Tryptophan Fluorescence in Various Proteins by a Chromium (III) Complex

ABSTRACT The interaction of a chromium (III) complex, (R,R)-N,N′-Bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diaminochromium (III), with human serum albumin, bovine serum albumin, lysozyme, and free tryptophan was studied using steady-state fluorescence spectroscopy. Dynamic and static quenching constants were calculated using Stern-Volmer kinetics. The complex bound more tightly to the serum albumins than to lysozyme or free tryptophan, but only one binding site was determined in all systems. The interaction was also determined to be thermodynamically favorable, and the binding constants were on the order of 103–106. The fluorescence quenching was static in nature with Forster distances in the 1.8–2.0 nm range.

Determination of oxygen permeabilities in thin polymer films using quenching of upconverted fluorescence in porphyrins

Proof-of-principle is demonstrated for a method of measuring the oxygen diffusion properties of thin polymer films based on quenching of the delayed upconverted S2 fluorescence of Zn(II) meso-tetraphenylporphine (ZnTPP). Empirical oxygen diffusion coefficients and permeability coefficients for poly(vinyl alcohol) (PVA) have been computed using Stern–Volmer kinetics in the steady-state regime and a nonlinear gas solubility model in the time domain. Simplified dual-mode theory has been used to calculate crude theoretical oxygen permeability coefficients to compare with the experimental values. It is confirmed that oxygen permeability in the PVA matrix is controlled largely by the characteristics of the polymer matrix, particularly its water content and distribution.

Efficient Photochemical Oxidation of Anisole in Protic Solvents: Electron Transfer driven by Specific Solvent–Solute Interactions

The dynamics of the bimolecular quenching of triplet excited benzophenone by anisole was studied by nanosecond flash photolysis. We carried out a detailed study of the solvent dependence of the reaction rates and efficiencies in a number of protic and non-protic solvents. These studies were augmented by theoretical modelling and experimental investigation of solute/solvent interactions in the triplet excited and the ground state, respectively. The triplet quenching that follows Stern-Volmer kinetics in all cases is profoundly dependent on the nature of the solvent, with the highest reactivity being consistently found in protic solvents. The results in non-protic solvents are compatible with unproductive quenching via a charge-transfer state, whereas the generally fast quenching in protic solvents is accompanied by efficient formation of free-radical products. Analysis of the solvent dependence in terms of Marcus theory reveals the impact of specific solvation of benzophenone by protic solvents on the ET driving force and kinetics. Specific solvation is found to support efficient free radical ion formation in media of moderate and low polarity as well.

Reductive Fluorescence Quenching of the Photoexcited Free Base meso-Tetrakis (Pentafluorophenyl) Porphyrin by Amines

Steady state and time resolved fluorescence quenching behaviors of meso-Tetrakis (pentafluorophenyl) porphyrin (H(2)F(20)TPP) in presence of different aliphatic and aromatic amines have been executed in homogeneous dichloromethane (DCM) solution. At room temperature in DCM, free base (H(2)F(20)TPP) shows fluorescence with two distinct peaks at 640 and 711 nm and natural lifetime tauf=9.8 ns which are very similar to that of meso-tetraphenyl porphyrin (TPP). Unlike TPP, addition of both aliphatic and aromatic amines to a solution containing H(2)F(20)TPP results in an efficient decrease in fluorescence intensity without altering the shape and peak position of fluorescence emission. Upon addition of amines there was no change in optical absorption spectra of H(2)F(20)TPP. The fluorescence quenching rate constants ranged from 1 x 10(9) to 4 x 10(9) s(-1), which are one order below to the diffusion control limit, and temperature dependent quenching rate constants yield the activation energies which are found to be order of 0.1 eV. Femto second transient absorption studies reveal the existence of amine cation radical and porphyrin anion radicals with very short decay time (15 ps). The fluorescence quenching reaction follows Stern-Volmer kinetics. Steady state and time-resolved data are interpreted within general kinetic scheme of Marcus semi-classical model which attributes bimolecular electron transfer process between amines and the lowest excited singlet state of H(2)F(20)TPP. Calculated internal reorganization energies are found to be in between 0.04 and 0.22 ev. Variation of electron transfer rate as function of free energy change (DeltaG(0)) points the ET reactions in the present systems are in Marcus normal region. This is the first example of reductive fluorescence quenching of free base neutral porphyrins in homogeneous organic solvent ever known.

On the quenching of MLCT luminescence by amines: The effect of nanoaggregation in the decrease of the reorganization energy

The MLCT luminescence quenching of pyRe(CO) 3bpy + and/or the polymer {[(vpy) 2-vpyRe(CO) 3bpy]CF 3SO 3} n–200 by amines proceeds via an electron transfer reaction which produces amine radical cations and pyRe I(CO) 3(bpy) /–Re I(CO) 3(bpy) , respectively. The quenching follows a typical Stern–Volmer kinetics for both pyRe(CO) 3bpy + and {[(vpy) 2-vpyRe(CO) 3bpy]CF 3SO 3} n–200 . The observed rate constants for the quenching of the Re I-polymer luminescence by amines show “vestiges” of the inverted effect predicted by Marcus while the quenching of pyRe(CO) 3bpy + luminescence follow the Rehm–Weller type of behavior. The lower value obtained for the total reorganization energy of the Re I-polymer than that for pyRe(CO) 3bpy + is rationalized in terms of the retarded solvent motions inside the nanoaggregates formed by the Re I-polymer in acetonitrile solutions.

A Spectroscopic Study of the Interaction of the Fluorescent β-Carboline-3-carboxylic Acid N-methylamide with DNA Constituents: Nucleobases, Nucleosides and Nucleotides

Interaction between beta-carboline-3-carboxylic acid N-methylamide, betaCMAM, and nucleobases, nucleosides and nucleotides is studied in the ground state with UV-visible, (1)H NMR and (31)P NMR spectroscopies and in the first excited state, with steady-state and time-resolved fluorescence spectroscopy. Job plots show a predominant 1:1 interaction in both electronic states. Association constants are estimated from changes in the absorption spectra, and show that the strongest interaction is produced with the nucleosides: 2'-deoxyadenosine (dAdo) and thymidine (Thd), and with the mononucleotides: 2'-deoxycytidine 5'- monophosphate (5'-dCMP) and uridine 5'- monophosphate (5'-UMP). These results are corroborated by the upfield shifts of two (1)H NMR resonances of the betaCMAM indole group. The (31)P NMR resonance of nucleotides is shifted downfield, suggesting the presence of electrostatic or hydrogen bond interaction with betaCMAM. In the first electronic singlet excited state, static and dynamic quenching of betaCMAM emission is achieved upon addition of nucleobases, nucleosides and nucleotides. This has been analysed using Stern-Volmer kinetics.

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 lambda(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.

Controlling the Color Space Response of Colorimetric Luminescent Oxygen Sensors

The color space response of colorimetric luminescent oxygen sensors is described in terms of the Commission Internationale de l'Eclairage (CIE) x,y color coordinates. We show how the color change response to oxygen can be obtained, provided the quenching kinetics for all lumophores involved can be represented mathematically. The theory is illustrated by analysis of examples of theoretical sensors in which lumophores are quenched by Stern-Volmer kinetics to give red to green, green to red, and red to green to blue color responses as the partial pressure of oxygen is increased. The effects of lumophore emission lifetime and the permeability of the polymer matrix to oxygen are discussed in terms of the control of sensor response, which variations in these parameters offer.