Deexcitation of Cd 53P1 atoms in collisions with ground state atoms and molecules

Collisions of excited Cd 5³P₁ atoms were investigated using atomic fluorescence spectroscopy. Cadmium vapor, together with a quenching gas, was irradiated in a quartz fluorescence vessel with Cd 3261 Å resonance radiation and the intensity of the resulting resonance fluorescence was monitored in relation to the gas pressures. The experiments yielded the following cross sections Q₁₀ (in A²) for collisional transfer 5³P₁→5³P₀: CdAr=2×10^?3, CdN₂=8.0, CdH₂=7.0, CdCO=15.6. The cross sections Q for collisional deexcitation to the ground state (quenching) in A² are CdN₂ = 2.6×10^?2, CdH₂ = 11.0, CdCO = 3.4, CdCO₂ = 26.     

Excitation transfer and quenching induced in inelastic collisions of cadmium 51P1 atoms

The quenching of excited Cd(5¹P₁) atoms induced in collisions with Ar, N₂, H₂, CO, and CO₂ has been investigated using methods of fluorescence spectroscopy. Mixtures of Cd vapor and quenching gases contained in a quartz cell were irradiated with 2288 Å resonance radiation and the fluorescence spectrum consisting of the 2288 Å direct component, as well as of the 3261 Å sensitized component, was monitored in relation to the gas density. The experiments yielded the following cross sections Q_tot for the overall collisional deexcitation of the ¹P₁ state, as well as the cross sections Q₁₃ for ¹P₁→³P_J excitation transfer (in Ų).For argon: Q₁₃ < 2 × 10^-2, for N₂: Q_tot =48.5, Q₁₃ =48.0; for H₂: Q_tot = 19, Q₁₃ = 7.2; for CO: Q_tot = 110, Q₁₃ = 15; for CO₂: Q_tot = 121, Q₁₃ < 6 × 10^-3.     

Quenching of excited strontium atomic state measured in H2- and CO-flames

The efficiency of resonance fluorescence, Y, of the strontium resonance line (¹P₁→¹S₀ transition) at 4607.33 Å was measured in CO/N₂O, CO/O₂/Ar, and H₂/O₂/CO₂/N₂ flames at atmospheric pressure. From these data, the specific quenching cross sections, σ_qu, for CO₂ and CO were found to be (60 ± 10) Ų and  (300 ± 60) Ų, respectively. The experimental cross sections were confronted with the intermediate ionic-state curve-crossing model and chemical quenching model, respectively.     

Kinetics of luminescence induced by sputtering metallic cadmium by a pulsed fast electron beam in helium

Results of an experimental study of the kinetics of luminescence observed when a metallic cadmium foil is bombarded in a helium medium by a 3-ns pulsed beam of 150-keV fast electrons are reported. The foil was irradiated at gas pressures from 76 to 2280 Torr. At a foil temperature of T = 240° C, the de-excitation time of the Beitler levels of the Cd II ion was measured as a function of the buffer gas pressure and the constant of collision quenching of the 5s22D_5/2 level of Cd II by He atoms was determined as k ≈ 3 × 10^-29 cm⁶/s. The experimental data were compared with calculations performed for the gas—vapor mixture in order to find the fraction of excited Cd II ions in the 5s²2D_5/2 state produced directly as a result of sputtering of metallic cadmium by high-energy electrons and by components of the helium plasma. At a helium buffer gas pressure of P ≤ 2.5 atm and a temperature of the cadmium target of T = 240° C, the value of this quantity was found to be α = 0.28 + 0.23P (where P is the helium pressure in atmospheres).     

Lifetime measurements,infrared and photoacoustic spectroscopy of NdP5O14

We have made a series of spectroscopic measurements to better understand the optical properties and concentration quenching characteristics of the stoichiometric laser material NdP₅O₁₄. The results of fluorescence lifetime measurements in the presence of different surface environments indicates that the surface condition affects the concentration quenching whereas lifetime measurements under applied uniaxial stress show that the presence of internal strains in the crystal is not significantly effective in fluorescence quenching. A comparison of the internal reflection spectrum with the normal infrared spectrum did not reveal any significant differences in the Nd³⁺ energy levels. Photoacoustic spectroscopy results proved difficult to interpret but appear to be consistent with the presence of surface quenching of excitons and indicate that the intrinsic quantum efficiency of Nd³⁺ ions in the pentaphosphate host in the absence of concentration quenching is approximately 0.90.     

Energy transfer from the singlet levels of diketones and dyes to lanthanide ions in nanoparticles consisting of their diketonate complexes

The energy transfer from the S ₁ levels of p-phenylbenzoyltrifluoroacetone (PhBTA) and dyes to different Ln³⁺ ions is studied in nanoparticles (NPs) composed of complexes of this diketone with Ln³⁺ and 1,10-phenanthroline (phen) and doped with dye molecules. The quenching rate constants in the NPs consisting from complexes of Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Ho³⁺, Er³⁺, and Tm³⁺ are determined from the data on the quenching of sensitized (cofluorescence) and ordinary fluorescence of coumarin 30 (C30) and rhodamine 6G (R6G). The quenching rate constants vary from ≤5 × 10¹¹ to 10¹³ s^?1 for the fluorescence quenching of PhBTA by different Ln³⁺ ions, while the quenching of dye fluorescence occurs at rates of the order of 10⁹ s^?1. In the case of complexes with the Pr³⁺ ions, the fluorescence quenching of PhBTA in NPs composed of its complexes is accompanied by sensitized luminescence of Pr³⁺. The quenching observed is due to a nonradiative energy transfer from the S ₁ states of ligands and dyes to these ions. It is shown that in NPs composed of complexes with Eu³⁺, Yb³⁺, and Sm³⁺ the cofluorescence of C30 is quenched via the electron-transfer mechanism. The study of quenching of cofluorescence and fluorescence of dyes in NPs composed of mixed complexes of La³⁺ and Nd³⁺ (Ho³⁺) shows that the observed quenching of fluorescence and cofluorescence is governed mainly by the quenching of the S ₁ state of dyes when the Nd³⁺ (Ho³⁺) content does not exceed 5–10% and by the quenching of the S ₁ state of a ligand when the Nd³⁺ (Ho³⁺) content exceeds 50%. It is assumed that the high rate constant of energy transfer from the S ₁ level of ligands to ions Pr³⁺, Nd³⁺, Ho³⁺, Er³⁺, and Tm³⁺ in NPs composed of beta-diketonate complexes is caused by exchange interactions.     

Determination of Copper(II) Ion Concentration by Lifetime Measurements of Green Fluorescent Protein

The understanding of cellular processes and functions and the elucidation of their physiological mechanisms is an important aim in the life sciences. One important aspect is the uptake and the release of essential substances as well as their interactions with the cellular environment. As green fluorescent protein (GFP) can be genetically encoded in cells it can be used as an internal sensor giving a deeper insight into biochemical pathways. Here we report that the presence of copper(II) ions leads to a decrease of the fluorescence lifetime (τ _fl) of GFP and provide evidence for Förster resonance energy transfer (FRET) as the responsible quenching mechanism. We identify the His₆-tag as the responsible binding site for Cu^2?+? with a dissociation constant K _d ?=?9 ±2 μM and a Förster radius R ₀?=?2.1 ±0.1 nm. The extent of the lifetime quenching depends on [Cu^2?+?] which is comprehended by a mathematical titration model. We envision that Cu^2?+? can be quantified noninvasively and in real-time by measuring τ _fl of GFP.     

Excitation transfer and quenching induced in inelastic collisions of Zn 41P1 and 43P1 atoms

Quenching of excited Zn(4¹P₁) and Zn(4³P₁) atoms by collisions with Ar, N₂, H₂, CO and CO₂ has been investigated using methods of fluorescence spectroscopy. Mixtures of Zn vapor and quenching gases topped-up with Ar to maintain constant pressure were irradiated in a quartz cell with 2139 or 3076 Å resonance radiation which excited the 4¹P₁ or the 4³P₁ state, respectively. The resulting resonance fluorescence and sensitized fluorescence were monitored in relation to the gas density. Intensity measurements yielded the following cross sections Q_tot for the overall collisional deexcitation of the ¹P₁ state, Q₃ for quenching of the ³P₁ state, and Q₁₃ for ¹P₁→³P_J excitation transfer.For N₂: Q_tot = 26, Q₃ = 4.4, Q₁₃ = 5.8; for H₂: Q_tot = 12, Q₃ = 21, Q₁₃ < 5 × 10^-3; for CO: Q_tot = 28, Q₃ = 14, Q₁₃ = 17; for CO₂: Q_tot = 76, Q₃ = 23. All values are in Ų.     

Laser-induced fluorescence of the CH molecule in a low-pressure flame

The laser-induced fluorescence from [A²Δ(υ′ = 0)→X²Π(υ″ = 0)] band of the CH radical was studied in a low-pressure (20 torr) methane-oxygen flame (φ = 1.06). A time-resolved fluorescence technique was used to measure the relative CH concentration profile and the quenching of the A²Δ excited state through the flame. The pressure dependence of the quenching was also measured and used to determine an effective quenching cross section of 6 Ų in the CH₄-O₂ flame. Analysis of the fluorescence spectra scanned at different delays after the laser excitation, according to a pseudo-three-level model, yields a rotational energy transfer (RET) rate in the A²Δ(υ′ = 0) electronic state which is a factor of four faster than the electronic quenching rate of 1.57 × 10⁷ sec^-1 in the flame at 2000 K.     

Experimental evidence about the mechanism of excitation transfer in mercury-cadmium sensitized fluorescence

By means of the magnetic scanning method, the author shows that the optical breadth of the sensitized fluorescence line (λ = 3261 Å) in a Hg-Cd mixture is about four times the breadth of the same line emitted by the ordinary optical resonance of cadmium. This result strongly suggests that Hg-Cd sensitized fluorescence is well described by the following equation: Hg(6³P₁) + Cd(5¹S₀) → Hg(6¹S₀) + Cd(5³P₁). It is in disagreement with the recent experimental result of Kraulinya et al. who suggest a more complex process involving molecular compounds.     

Fluctuation kinetics of the hopping fluorescence quenching in disordered solid solutions: A theoretical model and experimental evidence

Fluctuation kinetics of the hopping fluorescence quenching in disordered solid solutions is investigated for the first time. Measurements were made in the chelated complexes of rare-earth ions [Y_1−xTb_x(pyca)₃(H₂O)₂]nH₂O used as chromophore. The Tb³⁺ ions and the OH^--ions of unbounded water molecules appear as fluorescent donors and randomly distributed acceptors, respectively, with the dipole-dipole interaction between them. The measured fluctuation kinetics is the kinetics of the Förster type but with larger decay amplitude. It begins almost immediately after the initial static stage of quenching, and lasts for the entire interval of measurements leaving no room at all for the well-known exponential kinetics with constant rate. Proposed theoretical explanation of the phenomenon is based on the solution of the closed many-particle integral equation for the observable kinetics of hopping fluorescence quenching. The methods for determination of the energy transfer microparameters by the measured fluorescence quenching kinetics are discussed.     

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.     

Zeeman effect of the 6011 Å line of Pr3+: LaCl3 using the fluorescence line-narrowing technique

The Zeeman effect of the 6011 Å resonance line of Pr³⁺ in a LaCl₃ crystal has been studied by means of the fluorescence line-narrowing technique using a cw single-mode tunable laser. The experiments have confirmed the assumptions made previously to interpret the spectra in zero magnetic field. They have led to accurate values of the hyperfine structure constant and of the spectroscopic splitting g-factor of the ground level.     

Calcination temperature optimization,energy transfer mechanism and fluorescence temperature dependence of KLa(MoO4)2:Eu3+ phosphors

The optimum calcination temperature for KLa(MoO₄)₂:Eu³⁺ phosphor was confirmed to be 1000 °C via checking the XRD patterns, SEM images and fluorescence spectra for the samples derived from solid state reaction. The energy transfer behavior between Eu³⁺ ions was studied. It was found that electric dipole–dipole interaction is responsible for the fluorescence quenching of ⁵D₂ and ⁵D₁ levels, but exchange interaction is in charge of ⁵D₀ fluorescence quenching. It was also observed that color coordinates of the studied phosphor can be tuned when the doping concentration is relatively low. The fluorescence thermal quenching process was investigated. It was found the thermal quenching followed well crossover model. Judd–Ofelt parameters of Eu³⁺ in KLa(MoO₄)₂ were obtained, and the optical transition properties were further discussed.     

Luminescence and laser transition studies of Dy:K-Mg-Al fluorophosphate glasses

Dysprosium ion doped fluorophosphate glasses with compositions of PKMAFDy: (56−x/2) P₂O₅+17K₂O+8Al₂O₃+(15−x/2)MgO+4AlF₃+xDy₂O₃ (x=0.01, 0.05, 0.1, 1.0 and 2.0 mol%) have been prepared by melt quenching technique and are characterized by optical absorption, emission spectra and fluorescence lifetime measurements. The observed bands in the absorption spectrum are analysed by using free-ion Hamiltonian (H_FI) model. The Judd-Ofelt (JO) analysis has been performed and the intensity parameters (Ω_λ, λ=2, 4, 6) have been evaluated that are used to predict radiative properties. From emission spectra, the effective bandwidth (Δλ_eff) and the stimulated emission cross-section (σ(λ_p)) were evaluated. The fluorescence decay from the ⁴F_9/2 level of Dy³⁺ ions have been measured by monitoring the intense ⁴F_9/2→⁶H_13/2 transition (573 nm). The lifetimes (τ) are found to decrease with increasing concentration due to concentration quenching. The decay curves are single exponential for lower concentrations and gradually changes to non-exponential for higher concentrations. The non-exponential decay curves are well fitted to the Inokuti-Hirayama (IH) model for S=6 which indicates that the energy transfer between the donor and acceptor is of dipole-dipole type. The systematic analysis on decay measurements reveals that the energy transfer mechanism strongly depends on concentration as well as glass composition.     

Dynamic quenching of the multiband fluorescence of 3-hydroxyflavone

The properties of emission, absorption, and dual fluorescence excitation of 3-hydroxyflavone in acetonitrile are studied under the conditions of dynamic quenching by potassium iodide with concentrations up to 4 × 10^?2 M. The normal and tautomeric forms undergo quenching, which is more efficient for the tautomeric form. An interesting circumstance is that the absorption in the S ₀ → S ₁ and S ₀ → S ₂ singlet bands of the solution increases with increasing quencher concentration in the whole region of concentrations used, the steepest rise being recorded in the concentration region from 0 to 5 × 10^?3 M. The intensities and quantum yields of the two fluorescence bands show rather complicated nonlinear dependences on the quencher concentration. The long-wavelength fluorescence band, which belongs to the tautomeric form of 3-hydroxyflavone, is quenched considerably stronger. The experimental results reveal the kinetic character of the excited-state proton transfer in molecules of 3-hydroxyflavone in acetonitrile.     

A Novel Quinazolinone Derivative as Fluorescence Quenching Off-On Sensor for High Selectivity of Fe3+

A novel quinazolinone compound containing quinazoline-fused moiety has been synthesized as fluorescence Off-On sensor QQ. The probe exhibited highly selective and sensitive recognition toward trivalent ferric ion (Fe³⁺) over other metal ions in HEPES buffer solution (10 mM, pH?=?7.0, DMF-H₂O, 9:1, v/v). The significant quenching in the fluorescence spectral could be served as a selective fluorescence Off-On sensor. The titration study indicated the formation of 1:1 complex between QQ and Fe³⁺.     

Photoluminescence and decay behavior of Tb3+ ions in sodium fluoro-borate glasses for display devices

We report the optical absorption, photoluminescence and fluorescence decay properties of Tb³⁺-doped sodium fluoro-borate (SFB) glasses. Different concentrations of Tb³⁺-doped SFB glasses were prepared by conventional melt quenching technique using a chemical composition (in mol%) 25Na₂O–5LaF₃–10CaF₂–10AlF₃–(50?x) B₂O₃?x TbF₃ (0.01≤x≥4). The Judd-Ofelt model has been adopted to determine the radiative parameters of the ⁵D₄→⁷F_6–3 emission transitions. The effect of Tb³⁺ ion concentration on the emission from the ⁵D_3,4 excited levels is discussed in detail. The analysis of optimization of Tb³⁺ ion concentration for efficient green color display devises is reported. The resonance energy transfer mechanism responsible for non-radiative decay rates is clearly explored.     

Interaction of the flavonoid hesperidin with bovine serum albumin: A fluorescence quenching study

The interaction between the flavonoid hesperidin and bovine serum albumin (BSA) was investigated by fluorescence and UV/Vis absorption spectroscopy. The results revealed that hesperidin caused the fluorescence quenching of BSA through a static quenching procedure. The hydrophobic and electrostatic interactions play a major role in stabilizing the complex. The binding site number n, and apparent binding constant K_A, corresponding thermodynamic parameters ΔG^o, ΔH^o, ΔS^o at different temperatures were calculated. The distance r between donor (BSA) and acceptor (hesperidin) was obtained according to fluorescence resonance energy transfer. The effect of Cu²⁺, Zn²⁺, Ni²⁺, Co²⁺, and Mn²⁺ on the binding constants between hesperidin and BSA were studied. The effect of hesperidin on the conformation of BSA was analyzed using synchronous fluorescence spectroscopy and UV/Vis absorption spectroscopy.     

Thermal dependence of impurity induced fluorescence in the system RbMgxMn1-xF3

The absorption spectrum of RbMnF₃ and the excitation spectra of the system RbMg_xMn_1-xF₃ at 10 K as well as the fluorescence spectra and lifetimes of Mn²⁺ in the systems RbMg_xMn_1-xF₃ and KMg_xMn_1-xF₃ in the region 10–300 K were measured. The lifetime and fluorescence temperature dependence suggest that the origin of the fluorescence occurs at Mn²⁺ sites slightly perturbed by impurity ions and that a non-radiative energy transfer mechanism is responsible for the observed thermal quenching. By using different Mn²⁺ concentrations in the above systems the dependence of the energy transfer on the Mn²⁺ concentration is shown. Finally, a preliminary observation on laser stimulated Mn²⁺ luminescence in the system RbMg_xMn_1-xF₃ is reported.