Emission intensity of terbium(III) bound to benzene-carboxylic acid derivatives

The emission intensity of Tb³⁺ bound to phenol, catechol, resorcinol, benzoic acid, pyridine, nicotonic acid, phthalic acid, salicylic acid, and picolinic acid has been studied. Relative intensities of Tb³⁺ emission indicate that formation of a chelate ring is necessary to observe enhancement of the emission relative to that of Tb³⁺ alone in aqueous solution. The pH dependence of Tb³⁺ emission when bound to phthalic, salicylic, and picolinic acids were examined in detail and evidence was found which indicated that the geometry of the Tb³⁺ ion undergoes several changes as the solution pH is raised. The emission intensities and pH dependences are also found to depend on the ratio of ligand to metal, and this observation support the presence of polynuclear lanthanide complexes existing in solution.     

Multiphoton Ligand-Enhanced Excitation of Lanthanides

We describe multiphoton excitation of the lanthanides europium (Eu³⁺) and terbium (Tb³⁺) when these ions are complexed with nucleic acids, proteins, and fluorescent chelators. In all cases excitation occurs by multiphoton absorption of the sensitizers. For the nucleotide GDP and an oligonucleotide with several guanines, the sensitized emission of Tb³⁺ excited at 776 nm indicated a three-photon process. For Tb³⁺ bound to the wild-type troponin C and a single tryptophan mutant (26W), excitation at 794 nm was also close to a three-photon process. For lanthanide chelators containing various sensitizers, we observed three-photon excitation in the case of methyl anthranilate, a mixuture of two- and three-photon excitation for carbostyril 124, and a two-photon process with a coumarin derivative. In the case of coumarin-sensitized emission of Eu³⁺ varied from a two- to a three-photon process at wavelengths ranging from 780 to 880 nm. The sensitized luminescence also shows significantly higher photostability compared to the fluorescence from the organic fluorophores alone. These results suggest the use of multiphoton-induced sensitized lanthanide fluorescence in biochemistry and cellular imaging.On leave from the Institute of Experimental Physics     

Novel room temperature ionic liquid for fluorescence enhancement of Eu and Tb

The newly prepared ionic liquid, 1-butyl-3-methylimidazolium benzoate, ([bmim][BA]), was found to enhance the fluorescence of Eu³⁺ and Tb³⁺. The fluorescence enhancement resulted from a sensitization of the lanthanide fluorescence by the benzoate anion of the ionic liquid, [bmim][BA], and a reduction in the non-radiative channels in the non-aqueous environment provided by the ionic liquid. However, the fluorescence enhancement of the lanthanides in the ionic liquid was limited due to the operation of the inner filter effect, which resulted from the strong absorption of the benzoate. The inner filter effect was minimized by observing the Eu³⁺ fluorescence using a front face geometry and also by diluting the lanthanide-[bmim][BA] system, using another ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][Tf₂N]), as a solvent. In the case of Tb³⁺, the emission from the lanthanide was masked by the strong emission from the ionic liquid in the region 450-580 nm. The long lived Tb³⁺ emission was therefore observed using delayed gated detection, where an appropriate delay was used to discriminate against the short lived emission from the ionic liquid. The large fluorescence enhancement due to ligand sensitized fluorescence observed with [bmim][BA] diluted in [bmim][Tf₂N], leads to nanomolar detection of the lanthanides. This is, to the best of our knowledge, the first report of an ionic liquid being employed for ligand sensitized fluorescence enhancement of lanthanides.     

Spectroscopic study on the 4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine and its metal complexes

Multitopic ligand, 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine (pyterpy), has attracted growing attention because of its unique structural features, optical and electrochemical properties. Here, we report spectroscopic studies of pyterpy and its metal complexes in methanol solution. For the pure pyterpy, the ligand emission intensity increased with its concentration in the dilute solution, but decreased when its concentration was over 1.3×10⁻⁵ mol/l due to the concentration quenching. No significant influence on the ligand luminescence was observed for the Zn²⁺-pyterpy complex but strong luminescence quenching was observed for the electroactive Fe²⁺- and Co²⁺-pyterpy complexes. The lanthanide (Sm³⁺, Eu³⁺ and Tb³⁺) complexes of the pyterpy showed both ligand and lanthanide ion emissions, especially for the Tb³⁺-pyterpy complex, suggesting that the excited energy of pyterpy ligand could be efficiently transferred to the central Tb³⁺ ions. The luminescence was pH sensitive with the strongest emission in the neutral solution. The results indicated that the multitopic ligand of pyterpy could not only act as linkers for the metal-directed building blocks, but also act as optical materials with its own emission at about 364 nm and as light antenna for the lanthanide ions.     

Lanthanide-cored fluorinated dendrimer complexes: synthesis and luminescence characterization

Eu³⁺-, Tb³⁺- and Er³⁺-cored dendrimer complexes were prepared by self-assembly of three fluorinated dendrons, each with a carboxylate anion focal point, around the lanthanide ion. Energy transfer from the peripheral fluorinated phenyl moieties of the dendrons to the lanthanide cation was evidenced spectroscopically for Eu³⁺- and Tb³⁺-cored dendrimer complexes in solution. The excitation of perfluorinated aromatic groups was found to decay with ca. 0.7 ns and a longer decay time 10-13 ns was related to the coordination at the Ln³⁺ focal point. Luminescence from the lanthanide core decays with lifetime in the range 1-1.5 ms over a wide concentration range (μM-mM), similar to the luminescence decay time of the corresponding acetate ion complexes in D₂O. The main quenching mechanism of the lanthanide emission appears to be due to vibrations among surrounding C-H bonds of the intermediate shell of the flexible dendrimer scaffold. Antenna effect and energy harvesting from the surface of the dendrimer and transfer to the core was the main mechanism for luminescecnce in the dendrimer complexes with lanthanide cations.     

Spectroscopic Study on the Photophysical Properties of Lanthanide Complexes with Long Chain Mono-Docosyl Phthalate

Ortho phthalic anhydride was modified with long chain alcohol (1-docosanol) to its corresponding monodocosyl phthalate (22-Phth). Subsequently, three novel lanthanide (Eu³⁺, Tb³⁺, and Dy³⁺) complexes with the long chain monodocosyl phthalate were synthesized and characterized by elemental analysis and Infrared spectra. The photophysical properties of these complexes were studied in detail with ultraviolet-visible absorption spectra, low temperature phosphorescence spectra and fluorescent spectra. The triplet state energy of 22-Phth was determined to be around 25,000 cm⁻¹ from the maximum phosphorescent peak at 400 nm, suggesting 22-Phth is suitable for the sensitization of the luminescence of Eu³⁺, Tb³⁺, and Dy³⁺. The fluorescence excitation and emission spectra for these lanthanide complexes of the three ligands take agreement with the above predict from energy match principle.     

Energy transfer from Tb3+ to Eu3+ ions sorbed on SrTiO3 surface

The energy transfer at room temperature between Tb³⁺ and Eu³⁺ ions sorbed onto SrTiO₃ powders is investigated, using Time-Resolved Laser-induced Fluorescence Spectroscopy (TRLFS). Several published works deal with the energy transfer between two lanthanide ions in co-doped matrices but it is the first time that transfer processes between two lanthanide ions sorbed on a solid surface is reported. The results show that the energy transfer between sorbed Tb³⁺ and Eu³⁺ ions on strontium titanate is a non-radiative process and follows a dipole–dipole type interaction. Moreover, the higher the acceptor ions Eu³⁺ concentration, the more efficient the energy transfer.It is shown that no energy migration between the Tb³⁺ donor ions occurs. A formalism based on the model of Inokuti–Hirayama is used and allows one to fit the non-exponential Tb³⁺ fluorescence decay. It is thus possible to evaluate the critical radius (R₀) of the influence sphere of the sorbed Tb³⁺ ions. According to the previous works, two sorption sites are considered for the sorbed rare-earth. The calculated radii are similar to those obtained for other couples of donor–acceptor lanthanide ions reported in the literature.     

Thermal effect on multiphonon-assisted anti-Stokes excited upconversion fluorescence emission in Yb3+-sensitized Er3+-doped optical fiber

The temperature effect upon infrared-to-visible frequency upconversion fluorescence emission in Yb³⁺-sensitized Er³⁺-doped germanosilicate optical fibers excited with cw radiation at 1.064 μm is investigated. The experimental results revealed an eightfold enhancement in the visible upconversion emission intensity as the fiber temperature was increased from 17 °C to 180 °C. The fluorescence emission enhancement is attributed to the temperature-dependent multiphonon-assisted anti-Stokes excitation process of the ytterbium sensitizer. A theoretical approach that takes into account a sensitizer absorption cross-section, which depends on the phonon occupation number, has proven to agree very well with the experimental data Received: 6 April 1999 / Revised version: 27 August 1999 / Published online: 27 January 2000     

Room-temperature fluorescence quenching of indoles by trivalent lanthanide ions in dimethyl sulfoxide

Quenching of the room-temperature fluorescence excitation and emission spectra of indole, 3-carbinolindole, 5-methoxyindole, and 3-methylindole in dimethyl sulfoxide by trivalent lanthanide ions Ln³⁺ was interpreted in terms of dynamic interactions between (¹L_a, ¹L_b) states of indoles and Ln³⁺. The fluorescence lifetimes of these indoles vary from 5.3 to 8.4 ns, according to their structure. Quenching rate constants (k_Q) range between 2.6×10⁸ and 1.7×10¹⁰ M⁻¹s⁻¹. Values of k_Q are significantly larger for Eu³⁺ and Yb³⁺ than for other lanthanide ions.     

铋镓共掺的高浓度掺铒石英基光纤中铒离子团簇率的实验研究

使用MCVD法结合溶液掺杂技术制作了铒铋镓共掺的石英基光纤.根据光纤吸收谱，得出其中铒离子浓度是5.24×10²⁵/m³.然后提出了一种新的利用透射率测定掺铒光纤的团簇率的实验方法，该方法相比于以前的方法更简单有效.利用该方法，测得了自制铒铋镓共掺光纤中团簇率.通过与前人的结果相比较，充分说明铋和镓的掺入大大提高了铒离子在石英基光纤中的溶解度，抑制了铒离子形成团簇.     

铋镓共掺的高浓度掺铒石英基光纤中铒离子团簇率的实验研究

使用MCVD法结合溶液掺杂技术制作了铒铋镓共掺的石英基光纤.根据光纤吸收谱,得出其中铒离子浓度是5.24×10²⁵/m³.然后提出了一种新的利用透射率测定掺铒光纤的团簇率的实验方法,该方法相比于以前的方法更简单有效.利用该方法,测得了自制铒铋镓共掺光纤中团簇率.通过与前人的结果相比较,充分说明铋和镓的掺入大大提高了铒离子在石英基光纤中的溶解度,抑制了铒离子形成团簇. 关键词： 掺铒光纤 石英基光纤 团簇 高浓度     

Structure and photophysical behavior of 2,2′-bipyrimidine/lanthanide ion complexes in various environments

The photophysical behavior of 2,2′-bipyrimidine has been studied alone and in the presence of several lanthanide or other metal ions. This substance, which is employed as bridging ligand in homo- and hetero-dinuclear complexes, can form stable complexes with luminescent lanthanide ions like Eu³⁺ and Tb³⁺. Complexes precipitated from common solvents are crystalline with a structure that consists of discrete, centrosymmetric dinuclear entities with a planar ligand configuration. These complexes are strongly luminescent. Luminescence is sensitized by ligand-to-metal energy transfer. However, when the ligand and metal ions are mixed in an unconventional solvent, like a poly(ethylene glycol) oligomer, all reagents stay in solution and produce a different type of complex where only an enhanced ligand-centered fluorescence can be observed. It is possible that such fluorescence is emitted by 2,2′-bipyrimidine in a non-planar configuration. This behavior has also been observed with other heterocyclic ligands that can exist in different conformers, like terpyridine, and it may explain why some ligand-lanthanide complexes sometimes fail to sensitize efficient photoluminescence.     

Thermal and magnetic behavior of Angustifolia Kunth bamboo fibers covered with Fe3O4 particles

Several Angustifolia Kunth bamboo fibers, which have been previously treated with an alkaline solution, were coated with magnetite particles. The coating of the fibers was achieved by an in-situ co-precipitation method with Fe²⁺ and Fe³⁺in NaOH or NH₄OH. The fibers were evaluated by chemical analysis using atomic absorption (A.A.) technique, structural characterization by X-ray diffraction (XRD), thermal stability with thermo-gravimetric analysis (TGA) in nitrogen at temperature range between 23 °C and 800 °C and magnetic behavior using vibrating sample magnetometry (VSM) applying a magnetic field between −27 KOe and 27 KOe at room temperature. We found that the thermal stability and magnetization depend of the synthesis method used to cover the Angustifolia Kunth bamboo fibers. In addition, an improved magnetic response was observed when NaOH solution is used to generate the magnetite coating on the fiber surface.     

Broadband 2 μm emission and energy-transfer properties of thulium-doped oxyfluoride germanate glass fiber

High near-infrared transparency Tm³⁺-doped germanate bulk glass and fiber have been fabricated and 2 μm emission properties demonstrated. Energy-transfer processes in the germanate glass and fiber are discussed. The emission spectra are obtained from both bulk glass and fiber with the excitation of a 794 nm laser diode. The results indicate that the line width of the Tm³⁺:³F₄→³H₆ emission spectra measured in fibers is narrower than that of the bulk glass sample and shifts to longer wavelengths with increment of fiber length. The extended overlap integral method is used to calculate the microparameters of energy transfer and critical distance. A model is derived to better understand of the energy-transfer process of thulium ions in the germanate glasses responsible for emission at 2 μm. The study indicates that Tm³⁺-doped germanate fibers with a large core diameter has proved to be promising infrared optical and high-power level laser materials.     

Observation of upconversion fluorescence and stimulated emission based on three-photon absorption

The observations of three-photon-induced frequency-upconversion fluorescence and the highly directional stimulated visible emission in two dyes, 4-[p-(dicyanoethylamino) styryl]-N-methylpyridinium iodide (abbreviated as CEASP) and the complex of CEASP and Ce(NO₃) (abbreviated as CEASP-Ce), are reported. The photographs of the forward amplified spontaneous emissions spots, pumped by an optical parametric oscillator idler with a pulse width of 8 ns and a wavelength of 1.3 μ m, are shown. The upconversion fluorescence produced both in dimethyl formamide solution and 2-hydroxyethyl methacrylate (HEMA) polymer spans from green to red, with a cubic dependence on the pump light intensity. The experimental results imply that the existence of the lanthanide ion Ce^{3 +} sensitizes the nonlinear absorption and emission.     

Lanthanide ion induced formation of stripes domain structure in phospholipid Langmuir-Blodgett monolayer film observed by atomic force microscopy

Long-range ordered stripes domain structures were observed in Dipalmitoylphosphatidylcholine (DPPC) Langmuir-Blodgett monolayer film which was spread on the subphase of lanthanide ion (Eu³⁺) solution and transferred to a freshly cleaved mica substrate by vertical deposition. This novel phenomenon was discussed in terms of the competitive interaction of dipole-dipole and electrostatic interactions of the DPPC molecules combined with lanthanide ions with those DPPC molecules free of lanthanide ions.     

Preparation and Time-Resolved Luminescence Bioassay Application of Multicolor Luminescent Lanthanide Nanoparticles

Because highly luminescent lanthanide compounds are limited to Eu³⁺ and Tb³⁺ compounds with red (Eu, ~615 nm) and green (Tb, ~545 nm) emission colors, the development and application of time-resolved luminescence bioassay technique using lanthanide-based multicolor luminescent biolabels have rarely been investigated. In this work, a series of lanthanide complexes covalently bound silica nanoparticles with an excitation maximum wavelength at 335 nm and red, orange, yellow and green emission colors has been prepared by co-binding different molar ratios of luminescent Eu³⁺–Tb³⁺ complexes with a ligand N,N,N¹,N¹-(4′-phenyl-2,2′:6′,2′′-terpyridine-6,6′′-diyl)bis(methylenenitrilo) tetrakis (acetic acid) inside the silica nanoparticles. The nanoparticles characterized by transmission electron microscopy and luminescence spectroscopy methods were used for streptavidin labeling, and time-resolved fluoroimmunoassay (TR-FIA) of human prostate-specific antigen (PSA) as well as time-resolved luminescence imaging detection of an environmental pathogen, Giardia lamblia. The results demonstrated the utility of the new multicolor luminescent lanthanide nanoparticles for time-resolved luminescence bioassays.     

Lanthanide ions as fluorescent probes for the nucleotides

The lanthanide ions reacted with the nucleotides to form a complex in which the lanthanides served as sensitive fluorescent probes. By selectively exciting the nucleotide, the quantum efficiency of narrow-line lanthanide ion fluorescence can be calculated. Quantum efficiency values of 0.19 to 0.01 and 0.14 to 0.01 were obtained for Tb⁺³ and Eu⁺³ respectively. For Dy⁺³ and Sm⁺³ the values were too low to measure accurately for most nucleotides. The binding of the lanthanides to the nucleotides can be reversed by prolonged dialysis against chelating agents. Between pH 3 and pH 7 the complex precipitates and approaches a maximum of lanthanide ion fluorescence at pH 5.5.     

Density functional studies on lanthanide (III) texaphyrins (Ln-Tex2+, Ln = La,Gd, Lu): structure,stability and electronic excitation spectrum

Density functional calculations have been performed to study the molecular structure and chemical properties of selected lanthanide(III) texaphyrins (Ln-Tex²⁺, Ln = La, Gd, Lu). The lanthanide element is found to reside above the mean N₅ texaphyrin plane, and the larger the cation, the greater the observed out-of-plane displacement. It is concluded that the lanthanide cation is tightly bound to the macrocyclic skeleton, yielding a stable structure. However, the chemical properties of Ln-Tex²⁺ are found to be only slightly affected by the substitution of the lanthanide element. A low-energy LUMO is found for the Ln-Tex²⁺ (Ln = La, Gd, Lu), which are therefore easily reduced in an electron-rich environment. Two characteristic bands are obtained in the calculated electronic excitation spectrum (a high-energy band at 454–462 nm and a low-energy band at 681–686 nm). The intensity of the high-energy band is much larger than that of the low-energy one, yielding a rather unique spectral feature.     

Yb-doped yttria–alumino–silicate nano-particles based optical fibers: Fabrication and characterization

An efficient method to fabricate transparent glass ceramic fibers containing in-situ grown Yb³⁺ doped oxide nano-particles based on yttria–alumino–silicate glass is presented. These large-mode area Yb³⁺ doped fibers having a core diameter around 25.0 μm were drawn by a proper control over the involved process parameters; by this, the size of nano-particles was maintained within 5–10 nm. The main spectroscopic and laser properties of the fabricated fibers along with the nano-structuration results are reported. These results reveal that the developed method offers new scopes for the contemporary Yb³⁺ fiber based devices.