On the mechanism of rhodamine 6G fluorescence quenching

The fluorescence of the widely used TPF dye rhodamine 6G is quenched by photons of the ruby as well as the Nd-glass laser. Taking into consideration the polarisation of the ground- and excited-state absorptions of rhodamine 6G a simple model of quenching results. The main process is an S₁ absorption with subsequent leave of the ordinary rhodamine 6G singlet system. For Nd-laser photons the cross section of the concerned transition following from our quenching experiments is σS₁→S₂ = 1.2×10^-16 cm².     

Particular features of manifestation of energy migration toward impurity in nanoparticles of metal complexes

We measure the fluorescence quantum yields (q _fl) of complexes of Al, Sc, Y, In, Lu, and Gd with dibenzoylmethane in aqueous and isopropanol solutions at different concentration ratios of ions and dike-tone. We reveal that, for the examined solutions, qfl of complexes varies more than by two orders of magnitude under the influence of the heavy atom. It is found that a considerable decrease in q _fl and τ_fl of ligands of complexes of listed ions caused by the influence of heavy atoms weakly affects the intensity of sensitized fluorescence of Nile red and rhodamine 6G molecules introduced into nanoparticles from these complexes in aqueous solutions. The revealed result is explained by the comparability of the singlet exciton free path length and the dimension of nanoparticles under study. We show that a lower fluorescence intensity of heavy metal complexes makes it possible to decrease its contribution in the range of the cofluorescence maximum of rhodamine 6G and to monitor the occurrence of the dye in the aqueous solution down to the concentration of 0.05 nM. We show that, in nanoparticles from Eu complexes, further fluorescence quenching of dibenzoylmethane is observed, as well as the appearance of cofluorescence of rhodamine 6G, the intensity of which is comparable with its intensity in nanoparticles of other complexes. The appearance of this cofluorescence cannot be explained by the existence of S-S energy migration.     

Effect of soap on the fluorescent lifetime and quantum yield of rhodamine 6G in water

Addition of the soap ammonyx LO to a solution of 2 × 10^-4Mrhodamine 6G in water lengthens the fluorescent lifetime from 3.8 to 5 nsec, and increases the relative quantum yield by ≈ 1.5. Concentrations of soap and solute are those commonly used in cw rhodamine dye lasers. Comparisons are made with rhodamine 6G in ethanol solutions.     

Photophysical and laser characteristics of pyrromethene 567 dye: Experimental and theoretical studies

Narrow-band laser performance of alcohol solutions of pyrromethene 567 (PM567) and rhodamine 6G (RH6G) dye was investigated using a home-made GIG-configured dye laser, excited by the second-harmonic radiation (at 532 nm) of a pulsed Nd:YAG laser. Higher laser efficiency was observed with PM567 dye (∼23% peak) in comparison to the commonly used RH6G dye (16.5%), in spite of much lower fluorescence quantum efficiency of the PM567 (0.83) vis-à-vis RH6G (0.98) dye solutions in ethanol. First principle-based electronic structure calculations were performed on PM567 dye in the ground (S ₀) and excited states (S ₁) using density functional theory to elucidate the structure and photophysical properties of the dye.     

Comparative laser performances of pyrromethene 567 and rhodamine 6G dyes in copper vapour laser pumped dye lasers

Narrowband laser performances and photochemical stability of alcoholic solutions of pyrromethene 567 and rhodamine 6G dyes, under high-repetition rate copper vapour laser (at 510 nm), as well as, high-peak intensity Nd:YAG laser (at 532 nm) excitation have been investigated. We have observed that pyrromethene 567 dye solutions offer higher efficiency, wider tuning range, but lower photochemical stability and higher lasing threshold than that of rhodamine 6G dye solutions. An addition of about 100 mM DABCO, as a singlet oxygen quencher, in pyrromethene 567 dye solutions improved its photochemical stability close to that of rhodamine 6G. The observation of higher slope efficiency, in spite of higher threshold pump energy for pyrromethene 567 dye than that of rhodamine 6G dye solutions, was explained by a predictive model on gain characteristics of both dye solutions as a function of pump energy. PACS 42.55.Mv; 42.55.Rz; 42.70.Hj; 42.70.Jk     

The Fluorescence Properties of Three Rhodamine Dye Analogues: Acridine Red,Pyronin Y and Pyronin B

The fluorescence spectra, fluorescence quantum yield, and fluorescence lifetime of Acridine Red (AR), Pyronin Y (PYY), and Pyronin B (PYB) in aqueous and organic solvents were measured by steady state fluorescence, time-correlated single photon counting, and electronic absorption methods. The rate constants of radiation and non radiation process (k_f and k_ic) were calculated to elucidate the structural effect on the fluorescence mechanism. The data for each compound are compared with that of the corresponding rhodamine dye. AR showed significant longer lifetime and higher quantum yield than PYY and PYB, because the alkyls on N atom enhance the internal conversion (IC), the longer the alkyl the faster the IC. However, the structural variation does not alter the rate constant of radiation process (k_f) but does change k_ic significantly. The phenyl in Rhodamine B or Rhodamine 6G shows only a slight effect on the fluorescence properties. Ethanol is the solvent in which all five compounds exhibit longest lifetime and highest fluorescence quantum yield.     

Energy migration toward a dye in nanoparticles from complexes with short fluorescent state lifetimes

We have studied regular features of the fluorescence sensitization (cofluorescence) of coumarin 30 and rhodamine 6G introduced into nanoparticles from complexes Ln(PhBTA)₃phen, where PhBTA is p-phenylbenzoyltrifluoroacetone and Ln is a triply charged Pr, Nd, Sm, Eu, Er, or Yb ion, which absorbs in the fluorescence range of ligands of complexes and dyes. We show that both the cofluorescence intensities (I _cofl) of rhodamine 6G in nanoparticles from Sm and Eu complexes and the behavior of intensity I _cofl on the content of rhodamine 6G coincide with the corresponding data obtained for nanoparticles from La and Lu complexes doped with rhodamine 6G molecules. A considerable decrease in I _cofl of rhodamine 6G is observed only in nanoparticles from complexes Nd(PhBTA)₃phen. In nanoparticles from Pr, Nd, Sm, Eu, Er, and Yb complexes doped with coumarin 30, it has been observed that, depending on the choice of the central ion, I _cofl of coumarin 30 is 2 to 80 times lower compared to I _cofl of the dye in nanoparticles from La and Lu complexes. A separate analysis of the influence of these ions on the energy transfer from complexes to coumarin 30 and on the fluorescence intensity of coumarin 30 incorporated into nanoparticles from these ions showed that a decrease in I _cofl of coumarin 30 by a factor of 2?C20 occurs due to the reduction of ??_fl of ligands of complexes under the influence of the interaction with Pr, Nd, Sm, Eu, Er, and Yb ions. Since ??_fl of complexes La(PhBTA)3phen is ??2 ps, while that of complexes Gd(PhBTA)3phen is ??1 ps, then, in nanoparticles with a maximal decrease in I _cofl of coumarin 30, ??_fl of complexes is reduced to ??0.1 ps. It has been found that, in nanoparticles from complexes with this ??_fl, energy migration over complexes takes place. However, as distinct from nanoparticles from La, Lu, and Y complexes, the free path length of singlet excitons in nanoparticles from complexes of absorbing ions is smaller than the nanoparticle size.     

Attenuation and speckle modulation of laser light in dispersive dye-doped media: Competition of absorption and scattering processes

The effect of competition of laser light absorption and scattering in dispersive media (1 μm polystyrene microspheres in ethylene glycol) with added dye (rhodamine 6G) was studied under the condition of near-resonant absorption of probe light in the host medium (solution of rhodamine 6G in ethylene glycol). The parameters of speckle modulation of transmitted light (the average speckle intensity and the oscillation index) were applied for characterization of light transport in the probed scattering systems as a function of dye concentration. The increase in dye concentration does not cause the expected decay in the transmittance of the examined dispersive systems for 532 nm laser light, but results in the decrease of their turbidity. This effect is accompanied by the rise of the average intensity and the oscillation index of speckle-modulated light, and can be rationalized by partial matching of the real parts of refractive indices for the host medium and embedded scatterers. This interpretation was supported by statistical modeling of light transport through the examined scattering systems.     

等色染料离子对浮选光度法研究-四溴荧光素*罗丹明6G体系

本文研究了四溴荧光素（ＴＢＦ）、罗丹明６Ｇ（Ｒ６Ｇ）等色染料离子对浮选光度法测定锗、铂和铁的方法。首先将被测金属离子形成的［ＭｅＬｎ（Ｒ６Ｇ）ｍ］（Ｌ：配位体,ｍ、ｎ为整数）有机溶剂浮选物,用碱解析并反萃于水相。而后加入与罗丹明６Ｇ等色的四溴荧光素溶液继续浮选,将形成的等色染料离子对Ｒ６ＧＴＢＦ浮选物溶解于丙酮。于５３０ｎｍ处测定吸光度值。由于２ｍ个染料同时吸收同一波长的光,而提高了方法灵敏度。测定Ｇｅ、Ｐｔ和Ｆｅ的摩尔吸光系数均在１０５Ｌｍｏｌ－１ｃｍ－１以上     

Double-resonant second harmonic generation from surface coverages of nile-blue A

Second harmonic emission from a dye covered quartz surface has been observed in total internal reflection. Coverages with the dye nile-blue A yielded an increase in second harmonic output by several orders of magnitude as compared to coverages with rhodamine 6G. In the latter case only the harmonic light is at resonance with the S₀–S₂ transition of the adsorbed dye molecules, whereas for nile-blue A both, the fundamental and the harmonic frequency, are at resonance with the respective singlet transitions.     

Fluorescence properties of dyes adsorbed to silver islands,investigated by picosecond techniques

The fluorescence properties of dye molecules (rhodamine 6G and erythrosin) adsorbed on pure glass surfaces and on silver islands films are investigated by cw and picosecond time-resolved methods. On pure glass surfaces we observe concentration quenching below a critical intermolecular distance (reduction of the fluorescence power per molecule as well as shortened and non-exponential fluorescence decay). On silver islands films the shortening in fluorescence lifetime is more drastic and is nearly independent of the intermolecular distance. This behavior suggests an electrodynamic interaction between dye monomers and plasmons in the metal particles, modified by a damping influence of dye dimers.     

Laser dye stability

A figure-of-merit (FOM) consisting of the initial laser slope efficiency times the dye lifetime constant is used to compare the effect of a Pyrex light filter and the cover gas upon the output characteristics of six laser dye solutions. The FOM is found to improve using the Pyrex filter from 2-fold (coumarin 102 under air) up to 3800-fold (rhodamine 6 G under argon). In most cases, the use of argon in place of air for a coumarin dye not only improves the laser output, but also increases the lifetime constant. However, two of the coumarin dyes had an increase in lifetime under air as compared to under argon. This difference is explained in terms of the relative energy levels of the singlet and triplet states of these dyes. In order to measure long-lived dye solutions, a separate output-monitored linear flashlamp was used to degrade the solutions. The dye lifetime constants were corrected for changes in the output of this linear flashlamp. The relative output of this dye degradation flashlamp was found to depend upon the wavelength of the measurement and the position of the sensor along the length of the lamp. The variation in the output of several flashlamps is shown for lamps operating up to a total of 30 million flashes. The lifetime constants of the dye LD-490 measured by using the coaxial laser flashlamp was found to be comparable with, but lower than, the constants obtained from using the linear dye-degradation flashlamp.     

Efficient amplification of sub-picosecond pulses of a non-CW dye laser

Efficient amplification in a dye laser amplifier is investigated theoretically and experimentally. A five-level rate equation approach is considered including rotational relaxation of the dye molecules. The effects of the pump pulse duration and of the parameters of the input pulse are discussed. The results are compared with experimental data for 0.5 ps pulses of a pulsed dye laser. Conversion efficiencies >10% are achieved for a single pass amplifier using Nd:YAG pump pulses of 2 ns while an effective fluorescence lifetime of 1.7±0.2 ns is determined for the gain medium rhodamine 6G. The triple pass amplifier stage of the laser system achieves an energy conversion of 4% with 40 J output pulses.     

A study of the interaction of rhodamine 6G with DNA by spectrophotometry and probe microscopy

The interaction of rhodamine 6G with DNA was studied by the methods of spectrophotometry and scanning probe microscopy. It was ascertained that rhodamine 6G interacts with the DNA macromolecules by cooperative binding to the exterior surface of the polymeric chain. As a result, organic nanostructures form on the surface of the polymers. The number of dye molecules in the nanostructures is estimated. The distribution of these structures along the double helix of DNA and their merging into larger conglomerates is studied.     

Spectral and temporal characteristics of fluorescence of drops comprising dissolved dye excited by the IR laser radiation

Fluorescence of solutions of rhodamine 6G in the form of single drops of millimeter sizes excited by the intense IR and visible laser radiation (with duration of laser pulses of ∼10 ns and wavelengths of 1064 and 532 nm) is experimentally investigated. It was found that the power thresholds of fluorescence excitation for drops comprising the dissolved dye are, by an order of magnitude, less than for a cell with dissolved dye. The dichromatic drop fluorescence has been revealed, which is manifested through the occurrence of two maxima in the fluorescence spectrum of drops comprising dissolved rhodamine 6G. The first maximum coincides with that of the dye fluorescence spectrum, while the second maximum is shifted by ∼1000 cm⁻¹ and is on the slope of the fluorescence line profile. It is shown that the duration of drop fluorescence does not exceed the duration of the exciting pulse.     

A simple,efficient plastic dye laser

A simple efficient plastic dye laser is described. A conversion efficiency of 47% was obtained from Rhodamine 6G doped PMMA, when pumped by the second harmonic of a Q-switched Nd: YAG laser in a near longitudinal pumping configuration. Lifetime tests performed on 0.3 cm² surface area of plastic, indicates a drop in efficiency from an initial 47% to 25% after 3.2 × 10⁴ shots. By defocusing the pump beam and doubling the sample thickness, the lifetime increases to 1 million shots before the dye laser efficiency drops from an initial 35% to 25%, for a scanned area of 2 cm², similar results have been obtained with rhodamine B.     

A simplified method for synthesis of Fe3O4@PAA nanoparticles and its application for the removal of basic dyes

A simplified method for synthesis of polyacrylic acid-bound iron oxide magnetic nanoparticles (Fe₃O₄@PAA NPs) was reported. The as-prepared nanoparticles were characterized by TEM, FT-IR, VSM and XRD. Characterization results indicated that PAA was successfully introduced onto the surface of Fe₃O₄ and did not cause any changes in magnetic property. The Fe₃O₄@PAA NPs were used to adsorb rhodamine 6G (R6G) as a model basic dye pollutant from aqueous solution. Kinetics data and adsorption isotherms were better fitted by pseudo-second-order kinetic model and Langmuir isotherm, respectively. The adsorption equilibrium could be reached at about 20 min, showing that the as-prepared adsorbent exhibited extremely rapid adsorption rate. The aqueous solution of the Yellow River was chosen as the test sample, and the results showed that the magnetic adsorbent was efficient for the removal of the basic dye in the real sample.     

Sensitization of fluorescence of dye molecules in nanoparticles of metal complexes

We studied the dependence of absorption and fluorescence spectra of complexes of Al, In, Sc, Y, and La with dibenzoylmethane and naphthoyltrifluoroacetone, as well as the dependence of sensitized fluorescence of dyes in nanoparticles of these complexes, in relation to the water pH, the ratio between ions and diketones, and the ion selection. We showed that the ability of complexes of ions to form nanoparticles that efficiently sensitize dye molecules incorporated into them is determined by stability constants of these ions with organic ligands and by their ability to compete with the formation of hydroxy complexes of these ions. We found that nanoparticles consist of diketonates of different compositions and that Nile red incorporated into nanoparticles is an indicator of the dependence of the composition of nanoparticles on the selection of the central ion of complexes and conditions of their formation. We revealed that complexes M(diketone)(OH)₂ self-assemble into nanoparticles with an admixture of dye molecules and efficiently sensitize dyes upon excitation into absorption bands of complexes. We showed that, at concentrations of rhodamine 6G in water smaller than 50 nM, the use of a solution that contains 50 μM of Al(III), In(III), or Sc(III) + 50 μM of naphthoyltrifluoroacetone makes it possible to increase the sensitivity of the luminescence analysis by 20-fold for the presence of rhodamine 6G in an aqueous solution.     

罗丹明染料荧光猝灭法测定超痕量辣根过氧化物酶

在HAC-NaAC缓冲液中,辣根过氧化物酶催化H₂O₂氧化KI生成I₂,过量的I-可与I₂结合形成I-₃,而I-₃分别与罗丹明S(RhS), 罗丹明G(Rh6G), 罗丹明B(RhB)和丁基罗丹明B(b-RhB)反应导致四体系在580,580,554和554 nm处的荧光强度降低。在选择条件下,对于RhS,Rh6G,RhB,b-RhB四体系,辣根过氧化物酶的浓度分别在8～6 400,40～4 000,32～3 200,40～6 400 pg·mL-1范围内与其荧光猝灭强度成线性关系,其检出限分别为3.2,3.0,2.4,3.7 pg·mL-1。其中RhS催化体系较好,用于酶联免疫乙肝试剂盒中辣根过氧化物酶活力的测定,结果比较满意。     

Columinescence of dye molecules in nanostructures of metal ion complexes

The mechanism of columinescence (fluorescence sensitization) of dyes incorporated in nanostructures of metal complexes is studied. It is shown for the first time that the columinescence of dyes is due to the transfer of excitation energy from ligands and metal ions of complexes that form nanostructures. It is proven that the dye columinescence of rhodamine 6G (R6G) molecules incorporated into nanostructures of Al(DBM)₃phen, Al(DBM) _n (OH)_{6 ? 2n} , and Eu(DBM)₃phen (DBM is dibenzoylmethane) nanostructures is completely determined by the singlet excitation energy migration from ligands to R6G molecules. It is shown that, at small concentrations of R6G, the R6G columinescence intensity is lower in nanostructures of metal complexes with a high probability of S-T conversion and that this difference disappears at large concentrations of R6G. In the case of Nile blue (whose S ₁ level lies below the ⁵ D ₀ level of Eu(III)) incorporated in nanostructures of Eu(DBM)₃phen complexes, as well as in nanostructures of Al(DBM)₃phen and Gd(DBM)₃phen complexes with admixture of Eu complexes, we observed the S-S energy transfer from DBM to NB in addition to the delayed sensitized fluorescence of NB previously observed in nanostructures of Eu complexes, which was caused by the energy transfer from the ⁵ D ₀ level of Eu(III) to NB. At dye concentrations below 100 nM, the efficiency of NB sensitization due to the migration of singlet excitation energy from DBM is lower than in the case of the energy transfer from Eu(III) ions, while, at large concentrations of the dye, the S-S energy transfer successfully competes with the sensitization of NB by Eu(III) ions. The use of dye columinescence makes it possible to easily determine dye concentrations of 2–100 nM in solutions with standard spectrofluorimeters.