Ultrafast nonlinear optical properties of dye-doped PMMA discs irradiated by 40 fs laser pulses

The two-photon absorption (TPA) characteristics of PMMA discs doped with three different dyes were studied using an fs-pulsed Ti-Sapphire laser as the pump source, and employing the open-aperture Z-scan technique. TPA cross-sections obtained for PMMA doped with the dyes PM597, DCM and rhodamine 6G–rhodamine B (co-doped) were found to be equal to 24.7, 33.3 and 32.3 GM, respectively (1 GM=10^?50 cm⁴ s phot^?1 mol^?1). Furthermore, two-photon fluorescence was measured for the samples containing DCM and rhodamine 6G–rhodamine B (co-doped). Compared to the one-photon fluorescence spectrum, the peaks in the two-photon fluorescence spectrum were red shifted and the extent of red shift increased with increasing doping concentration. We have also observed that the red shift in the two-photon fluorescence peak of the samples in the solid form is much larger than that in the solution state. This phenomenon could be explained by a twisted intra-molecular charge transfer model.     

Electronic states of the CeO molecule: Absorption,emission, and laser spectroscopy

The electronic spectrum of the CeO molecule is characterized by the existence of many 0-0 bands resulting from transitions between various Ω components of excited states and the 16 lower Ω states which arise from the lowest configuration… (4f)(6s). Classical studies of rotational structure of absorption and emission spectra have been extended, and argon-ion and tunable dye (coumarin 460, rhodamine 6G, rhodamine 101) lasers have been used to excite known transitions in bands which had previously been rotationally analyzed. The resulting fluorescence spectra have been used to establish the relative energies of the lower states. By tuning the lasers to excite analyzed transitions from different known electronic states it has been possible to determine the energies of 16 low-lying states, to assign quantum numbers to 14 with certainty, and to suggest assignments for the other 2. The resulting energy level diagram of lower states is discussed and shown to correlate well with the 4f6s configuration of the Ce²⁺ ion. From the energies of the low-lying states, those of the higher excited states are calculated and in some cases new values of vibrational and rotational constants are derived.     

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.     

Study of energy transfer in a solution of coumarin 460 and rhodamine 6G by time-resolved laser-induced fluorescence spectroscopy

A multi-photon fast analog technique has been used to study nonradiative energy transfer from coumarin 460 to rhodamine 6G molecules. At low acceptor concentrations (<10^-2 mol/1) the fluorescence decay from coumarin deviates markedly from monoexponential behavior. The complex decay of the donor fluorescence reflects the time-dependent population of donor-acceptor pairs. Various energy transfer kinetics were investigated. The donor decay was found to be consistent with Förster kinetics and the critical energy transfer radius was found to be (5.46±0.10) nm.     

Diffusion Coefficients of Several Rhodamine Derivatives as Determined by Pulsed Field Gradient–Nuclear Magnetic Resonance and Fluorescence Correlation Spectroscopy

Rhodamine derivatives are popular, photostable fluorophores that are used in a number of fluorescent based techniques, including fluorescence correlation spectroscopy (FCS). Indeed, in FCS, both rhodamine 6G (R6G) and rhodamine 110 (R110) are used as calibration standards to determine the dimensions of the instrument confocal volume. In spite of a requirement for precise values of the diffusion coefficients, literature values are scarce and vary over an order of magnitude. In this paper, the diffusion coefficients of four rhodamine fluorophores (rhodamine 6G (R6G), rhodamine B (RB), rhodamine 123 (R123), rhodamine 110 (R110)) were determined by pulsed field gradient nuclear magnetic resonance (PFG-NMR) spectrometry and then validated by comparison with fluorescence correlation spectroscopy. With the objective of validating the FCS calibration, diffusion coefficients of several dextrans and a polystyrene nanoparticle were also determined and compared with literature values or theoretical values that were based upon the Stoke–Einstein equation. The work presented here lead us to conclude that the diffusion coefficients for R6G and R110 have generally been underestimated in the literature. We propose revised values of 4.4 × 10⁻¹⁰ m² s⁻¹ for R110 and 4.0 × 10⁻¹⁰ m² s⁻¹ for R6G. Using the revised D value for R110 to calibrate the FCS instrument, diffusion coefficients have then been systematically determined for different conditions of pH, ionic strength and concentration. To correct for differences due to solvent effects (D₂O vs. H₂O), an isotopic correction factor, of 1.23, was determined from both FCS and from the solvent auto-diffusion coefficients obtained by NMR.     

Influence of the shape of the exciting laser pulse on fluorescence saturation in the quantitative analysis of dissolved trace organic substances

Theoretical investigations of the influence of the exciting laser pulse shape on fluorescence saturation in the quantitative analysis of a single-component fluorescing solution, when the Raman signal of the solvent is usedas a reference, are carried out. A quantity α is introduced, responsible for the influence of laser pulse shape on the precision of the analysis. The dependences of α on the exciting radiation photon flux density I_m in the range I_m = 10²² ? 10²⁸ photons/cm²?s and on the duration of the exciting pulses τ_p in the range τ_p = 0.6 ? 60 ns are computed for different pulse shapes in the case of rhodamine 6G dissolved in water. Conditions when α is, in practice, independent of τ_p and of the pulse shape are found. A general analytical expression is found for α, which produces errors not greater than several percent when compared to the computed values of α. An experimental verification of the theoretical results in the case of a rectangular-shaped pulse in the spatial domain and a Gaussian-shaped pulse in the temporal domain is realized.     

Phase-modulation fluorometer using a phase-modulated excitation light source

We propose a phase-modulation fluorometer (PMF) with a light-emitting diode (LED) or a laser diode (LD) used as an excitation light source (ELS) that is driven in the phase-modulation (PM) mode. The PM-ELS generates many frequency sidebands that spread in the vicinity of carrier frequency f _c with the interval of modulation frequency f _m depending on the maximum phase deviation Δφ. The scheme enables us to derive fluorescence lifetime values of a multicomponent sample at one time. We show a typical numerical simulation result for explaining the principle of operation. To demonstrate the effectiveness of the proposed PMF, we have measured fluorescence lifetimes of three kinds of inorganic fluorescent glasses and that of a mixture solution of 1 × 10^?6M rhodamine 6G and 1 × 10^?6 M coumarin 152 in ethanol with a volume ratio of 1: 1.     

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.     

Fluorescence behaviour of highly concentrated rhodamine 6G solutions

The fluorescence quantum distributions E(λ) and fluorescence quantum efficiencies q_F of rhodamine 6G in methanol and in water are measured for various concentrations up to the solubility limit. The fluorescence spectra are separated in monomer and dimer (ground-state dimer and closely spaced pair) contributions. The stimulated emission cross sections for the monomers and the dimers are resolved.     

Testing Fluorescence Lifetime Standards using Two-Photon Excitation and Time-Domain Instrumentation: Rhodamine B,Coumarin 6 and Lucifer Yellow

Having good information about fluorescence lifetime standards is essential for anyone performing lifetime experiments. Using lifetime standards in fluorescence spectroscopy is often regarded as a straightforward process, however, many earlier reports are limited in terms of lifetime concentration dependency, solvents and other technical aspects. We have investigated the suitability of the fluorescent dyes rhodamine B, coumarin 6, and lucifer yellow as lifetime standards, especially to be used with two-photon excitation measurements in the time-domain. We measured absorption and emission spectra for the fluorophores to determine which wavelengths we should use for the excitation and an appropriate detector range. We also measured lifetimes for different concentrations, ranging from 10^?2– 10^?6 M, in both water, ethanol and methanol solutions. We observed that rhodamine B lifetimes depend strongly on concentration. Coumarin 6 provided the most stable lifetimes, with a negligible dependency on concentration and solvent. Lucifer yellow lifetimes were also found to depend little with concentration. Finally, we found that a mix of two fluorophores (rhodamine B/coumarin 6, rhodamine B/lucifer yellow, and coumarin 6/lucifer yellow) all yielded very similar lifetimes from a double-exponential decay as the separate lifetimes measured from a single-exponential decay. All lifetime measurements were made using two-photon excitation and obtaining lifetime data in the time-domain using time-correlated single-photon counting.     

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.     

Phase transition of BiVO4 nanoparticles in molten salt and the enhancement of visible-light photocatalytic activity

BiVO₄ nanoparticles are prepared by molten salt method. Tetragonal BiVO₄ completely transforms to monoclinic phase after heating in molten LiNO₃ at 270 °C for 18 h. The average particle sizes of monoclinic BiVO₄ varied from 30 to 52 nm while the initial ratio of BiVO₄ to LiNO₃ changes from 1:6 to 1:24. The photocatalytic activity is evaluated by measuring decolorization of N,N,N′,N′-tetraethylated rhodamine dye solution under visible-light irradiation. Both of the de-ethylation and chromophore cleavage are responsible for the decolorization of RB. The sample with an average particle size of 52 nm and a moderate surface area of 10 m²/g exhibit the highest visible-light photocatalytic activity. The shift of Raman peak position indicates that the symmetry distortions in the local structure of the monoclinic BiVO₄. The variations of the local structure result in the modification of the electronic structure, which is responsible for the high visible-light photocatalytic activity.     

Ultrasound-assisted synthesis of graphene@MXene hybrid: A novel and promising material for electrochemical sensing

To date, multiple graphene@MXene hybrids have been reported via various synthesis approaches, but almost all the graphene@MXene hybrids inevitably used the reduced graphene oxide that prepared by chemical oxidation/reduction method, which generally involved the complex and dangerous operation procedure, and the highly toxic chemical reagent. How to prepare graphene@MXene hybrid through a simple, safe and eco-friendly synthetic route is highly desired. Compared with traditional synthesis technology, ultrasound synthesis strategy displays the merits of simplicity, low cost and environment protection. Herein, MXene (Ti₃C₂T_x) nanoflakes coupled with graphene nanosheets (graphene@MXene) were prepared in N-methylpyrrolidone (NMP) by simple ultrasound-assisted liquid-phase exfoliation method for the first time. Besides, the effect of types of solvent with different viscocity, sonication temperature and sonication duration time on the property of graphene@MXene hybrids were systematacially investigated. It is found the liquid-phase exfoliated graphene owned excellent electron transfer ability and the MXene (Ti₃C₂T_x) nanoflakes possessed outstanding adsorption property, the as-synthesized graphene@MXene hybrid exhibited significant signal synergistic enhancement effect toward the oxidation of hazardous veterinary drug residue compound (chlorpromazine) and food additives (rhodamine B). Based on this, a novel and sensitive electrochemical sensor was fabricated, the linear detection ranges were 5 nM to 0.5 μM for chlorpromazine with sensitivity of 1090 µA μM⁻¹ cm⁻², and 10 nM to 2.5 μM for rhodamine B with sensitivity of 440 and 102.14 µA μM⁻¹ cm⁻². Besides, the detection limits were evaluated to be as low as 1.25 nM and 2.45 nM for chlorpromazine and rhodamine B, respectively.     

An Efficient Fluorescence “Turn-On” Chemosensor Comprising of Coumarin and Rhodamine Moieties for Al<Superscript>3+</Superscript> and Hg<Superscript>2+</Superscript>

A potent fluorescence ‘turn-on’ receptor (HL) based on rhodamine and coumarin moieties for the detection of Hg²⁺ and Al³⁺ is synthesized by condensation of rhodamine 6G hydrazide and 4-hydroxy-3-acetylcoumarin. In presence of Al³⁺ and/or Hg²⁺ the receptor (HL) exhibits deep pink colouration and a sharp band at 528 nm is appeared in UV–vis titration. Upon gradual addition of Al³⁺ and/or Hg²⁺ to the solution of HL significant enhancement of fluorescence intensity is observed at 564 nm in MeCN:H₂O (1:5, v/v) medium. The receptor is strongly bound to Al³⁺ and/or Hg²⁺ and the association constants (K_a) are found to be 1.74?×?10⁴ and 1.04?×?10⁴ M^??1 for Al³⁺ and Hg²⁺ respectively.

Open image in new window

Graphical Abstract A potent fluorescence ‘turn-on’ receptor (HL) based on rhodamine and coumarin moieties for the detection of Hg²⁺ and Al³⁺ is synthesized and characterized. In presence of Al³⁺ and/or Hg²⁺ the receptor (HL) exhibits deep pink colouration and significant enhancement of fluorescence intensity is observed at 564 nm in MeCN:H₂O (1:5, v/v) medium. The receptor is strongly bound to Al³⁺ and/or Hg²⁺ and the association constants (K_a) are found to be 1.74?×?10⁴ and 1.04?×?10⁴ M^??1 for Al³⁺ and Hg²⁺ respectively.

     

Fourier transform infrared spectral study of N,N′-dimethylformamide-water-rhodamine 6G mixture

Infrared absorption spectra of N,N′-dimethyl formamide in the absence and presence of water, rhodamine 6G and water–rhodamine 6G mixture are reported. Assignment of observed bands has been made on the basis of density functional theory calculations and available assignments in the literature. Certain bands show changes in their positions and intensities when water is added to N,N′-dimethylformamide. This is due to hydrogen bonding interaction between these molecules. Similar changes are also observed for dimethylformamide and Rh6G mixture to a lesser extent. The presence of Rh6G in a dimethylformamide–water mixture reverses these spectral changes due to preferential solvation of Cl^? by water molecules. Solvation reduces or nullifies the hydrogen bonding between dimethylformamide and water in the mixture.     

Fluorescence Sensors for Selective Detection of Hg2+ Ion Using a Water-Soluble Poly(vinyl alcohol) Bearing Rhodamine B Moieties

The novel water-soluble poly(vinyl alcohol) with pendant rhodamine B moiety as colorimetric and fluorescene chemosensor for Hg²⁺ ions was prepared by grafting poly(vinyl alcohol) using rhodamine B hydrazide and hexamethylenediisocyanate as fluorescent dye and coupling agent, respectively. Because of their good water-solubility, the polymers binding rhodamine B can be used as chemosensors in aqueous media. With the addition of Hg²⁺ ions into the aqueous solution, visual color changes and fluorescence enhancements were detected. In addition, we also noticed that other metal ions such as Ag⁺, Cd²⁺, Co²⁺, Cu²⁺, K⁺, Mg²⁺, Ba²⁺, Fe²⁺, Ni²⁺, Pb²⁺, Cr³⁺, Fe³⁺ and Zn²⁺ cannot induce obvious changes to the fluorescence spectra of the polymer chemosensors. The combination of water solubility and positive fluorescence response as well as color change are hence particularly promising for the practical utility of the sensors.     

Luminescent spectral properties of rhodamine derivatives while binding to serum albumin

We have studied the effect of blood serum albumin on the absorption and fluorescence spectra of rhodamine C (RC), rhodamine 6G (R6G), and rhodamine 3B (R3B). Interaction of the dye with protein is assessed using the binding parameters: binding constants and concentrations of binding sites. We have studied the effect of temperature on the binding parameters. We have observed that heating a mixture of the dye solution with protein for 30 min leads to an increase in the binding constant for rhodamine 3B with protein by a factor of 2, while the concentration of binding sites increases by a factor of 2.3. This is explained by features of the globular protein structure and a change in its conformation when heated. We have shown that rhodamine 3B at a concentration of 10⁻⁵ M is the most effective among the studied rhodamine dyes for application as a fluorescent probe when studying conformational changes in blood serum protein. Report given at the Third International Conference on Liquid State Physics: Current Problems, May 27–31, 2005, Kiev, Ukraine. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 380–384, May–June, 2006.     

A Dansyl-Rhodamine Ratiometric Fluorescent Probe for Hg<Superscript>2+</Superscript> Based on FRET Mechanism

Based on resonance energy transfer (FRET) from dansyl to rhodamine 101, a new fluorescent probe (compound 1) containing rhodamine 101 and a dansyl unit was synthesized for detecting Hg²⁺ through ratiometric sensing in DMSO aqueous solutions. This probe shows a fast, reversible and selective response toward Hg²⁺ in a wide pH range. Hg²⁺ induced ring-opening reactions of the spirolactam rhodamine moiety of 1, leading to the formation of fluorescent derivatives that can serve as the FRET acceptors. Very large stokes shift (220 nm) was observed in this case. About 97-fold increase in fluorescence intensity ratio was observed upon its binding with Hg²⁺.     

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.     

Molecular gases as a source of coherent,tunable XUV radiation

Coherent and broadly tunable over 3500 cm^-1 extreme ultraviolet (XUV) radiation from 935 to 967 Å has been generated by frequency tripling the second harmonic output of a rhodamine 590 pulsed dye laser in molecular nitrogen and carbon monoxide. The scheme exploits high lying Rydberg and valence states of these gases and leads to the production of about 5 × 10⁹ XUV photons per pulse corresponding to a conversion efficiency of 5 × 10^-6.