Energy transfer processes and structure of carboxymethyl cellulose-Tb/Eu nanocomplexes with color-tunable photoluminescence.

A series of fluorescent nanocomplexes of carboxymethyl cellulose (CMC)/Terbium (Tb)- Europium (Eu) were successfully synthesized without introducing a second ligand. By adjusting the concentration of the coordinated ions, these nanocomplexes exhibit favorably visibly tunable luminescence properties with colors being able to change from green to red. The XPS analysis demonstrates the formation Tb(III)-O2- and Eu(III)-O2- between OH and COO- in CMC and Tb3+ or Eu3+ ions, which is advantage for light absorption by UV-Vis spectroscopy and fluorescence spectroscopy. The ligand CMC plays a role in coordinating with terbium and europium ions, but also serves as an energy donor to these metal ions by antenna effect. Moreover, the energy transfer also occurred from terbium ions to europium ions in CMC matrix, which is responsible for the tunable luminescence properties of these complexes.

Ferrocene Functionalized Upconversion Nanoparticle Nanosystem with Efficient Near-Infrared-Light-Promoted Fenton-Like Reaction for Tumor Growth Suppression.

By taking advantage of the efficient Förster resonance energy transfer (FRET) between near-infrared (NIR)-responsive lanthanide-doped upconversion nanoparticles (UCNPs) and Fenton reagent ferrocenyl compounds (Fc), a series of Fc-UCNPs was designed by functionalizing NaYF4:Yb,Tm nanoparticles with Fc1-Fc5 via surface-coordination chemistry. Fc-UCNP-Lipo nanosystems were then constructed by encapsulating Fc-UCNP inside liposomes for efficient delivery. Fc-UCNP can effectively release ·OH via a NIR-promoted Fenton-like reaction. In vitro and in vivo studies of Fc1-UCNP-Lipo confirmed the preferential accumulation in a tumor site followed by an enhanced uptake of cancer cells. After cellular internalization, the released Fc1-UCNP can effectively promote ·OH generation for tumor growth suppression. Such a Fc1-UCNP-Lipo nanosystem exhibits advantages such as easy fabrication, low drug dosage, and no ferrous ion release.

Dual-Signal Luminescent Detection of Dopamine by a Single Type of Lanthanide-Doped Nanoparticles.

Detection of dopamine, an important neurotransmitter, is vital for understanding its roles in mammals and disease diagnosis. However, commonly available methods for dopamine detection typically rely on a single signal readout, which can be susceptible to interference by internal or external factors. Here, we report a dual-signal detection of dopamine based on label-free luminescent NaGdF4:Tb nanoparticles. In the presence of dopamine, the NaGdF4:Tb nanoparticles exhibit luminescence quenching under the excitation of 272 nm, while they give enhanced luminescence under 297 nm excitation, realizing both turn off and turn on detection of dopamine. The nanoparticle-based dual-signal sensors exhibit high sensitivity, with a detection limit of ∼30 nM, and good selectivity, which offers the possibility to identify potential interferents in the samples. We further demonstrate that the dual-signal response results from different energy-transfer processes within the nanoparticles under the excitation of different light. The new strategy demonstrated here should pave the way for the development of multiresponse nanosensors based on lanthanide-doped luminescent nanomaterials.

Study of yellow luminescence of binary terbium complexes based on 3,3',4,4'-biphthalic anhydride.

Three novel binary Tb(III) complexes (TbL2, TbL, and Tb2L; L=3,3',4,4'-biphenyl tetracarboxylic ligand) were synthesized by changing the molar ratio of Tb(III) to 3,3',4,4'-biphthalic anhydride (BPDA) (1∶2, 1∶1, and 2∶1, respectively). IR spectra indicate that there are two coordination modes of the carboxylate ligands with Tb3+ ions in the complexes. Most of them are in bridging mode; the others are in chelating mode. These complexes all have good thermal stability. The photophysical properties of these complexes are studied in detail using UV absorption spectra, fluorescence spectra, and transient fluorescence spectra. The results indicate that the photoluminescence properties of the complexes depend strongly on the molar ratio of Tb(III) to BPDA. When the molar ratio of Tb(III) to BPDA is 1∶1, complex TbL exhibits the strongest yellow light emission among the three Tb(III) complexes. However, complex Tb2L exhibits a weaker yellowish-green light emission when the molar ratio of Tb(III) to BPDA is 2∶1. The phenomenon of the yellow emission from terbium complexes is rarely reported.

Contrasting behaviour of the co-activators in the luminescence spectra of Y2O2S:Tb3+,Er3+ nanometre sized particles under UV and red light excitation.

Nanometre sized particles of terbium and erbium co-doped yttrium oxysulfide up-converting phosphors were prepared by a urea homogeneous-precipitation method. Results from X-ray powder diffraction (XRPD), scanning electron microscopy (SEM) and photoluminescence spectroscopy studies on the microstructure and luminescent properties of the materials are reported. Upconversion emission was observed from the Er(3+) cations when particles were excited with laser light of 632.8 nm wavelength. Under these conditions no interactions between the Er(3+) cations and the Tb(3+) cations were observed. In contrast there was evidence from the Stokes emission of the Er(3+) cations under 254 nm excitation for an interaction between the Er(3+) and Tb(3+) cations reducing intensity of the latter's blue and green emission bands by cross relaxation processes.

Efficient near-UV photosensitization of the Tb(III) green luminescence by use of 2-hydroxyisophthalate ligands.

The first examples of lanthanide complexes with a 2-hydroxyisophthalate ligand are reported; the blue-emitting ligand acts as a very efficient sensitizer of the Tb(III) green emissions and does so in the near-UV region.

Lanthanide-binding tags with unnatural amino acids: sensitizing Tb3+ and Eu3+ luminescence at longer wavelengths.

Lanthanide-binding tags (LBTs) are small, genetically encoded, versatile protein fusion partners that selectively bind lanthanide ions with high affinity. The LBT motif features a strategically positioned tryptophan residue that sensitizes Tb3+ luminescence upon excitation at 280 nm. Herein, we describe the preparation of new LBT peptides that incorporate unnatural amino acids in place of tryptophan, and which sensitize both Tb3+ and Eu3+ luminescence at lower energies. We also report the semisynthesis of proteins tagged with these new LBTs using native chemical ligation. This expands the scope of LBTs and will enable their wider use in luminescence applications.

Luminescence studies on RbI:Tb3+ crystals.

Optical absorption, photoluminescence, thermoluminescence (TL) and photostimulated luminescence (PSL) studies on RbI:Tb(3+) crystals irradiated with gamma-rays is reported. Photoluminescence of these crystals exhibits characteristic Tb(3+) emissions, due to transitions from the (5)D(3) and (5)D(4) levels to various levels of the (7)F septet. On F-bleaching the gamma-irradiated crystals, Z(3) centres are observed. The TL glow curve indicates a two-step thermal annihilation process for the radiatively created defects. The presence of the characteristic emissions due to terbium ions in the photostimulation at the F-band, and TL emissions under both glow peaks, confirm the participation of Tb ions in the defect production and recombination processes. Trap parameters for the TL process are calculated and presented. The low temperature glow peak is attributable to Z(3) centres.

Nanostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles: polyol-mediated synthesis and luminescent properties.

Nano-submicrostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles were prepared by polyol method and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared spectra (FT-IR), thermogravimetry-differential thermal analysis (TG-DTA), photoluminescence (PL), cathodo-luminescence (CL) spectra and PL lifetimes. The results of XRD indicate that the as-prepared samples are well crystallized with the scheelite structure of CaWO4. The FE-SEM images illustrate that CaWO4 and CaWO4 : Pb2+ and CaWO4 : Tb3+ powders are composed of spherical particles with sizes around 260, 290, and 190 nm respectively, which are the aggregates of smaller nanoparticles around 10-20 nm. Under the UV light or electron beam excitation, the CaWO4 powders exhibits a blue emission band with a maximum at about 440 nm. When the CaWO4 particles are doped with Pb2+, the intensity of luminescence is enhanced to some extent and the luminescence band maximum is red shifted to 460 nm. Tb(3+)-doped CaWO4 particles show the characteristic emission of Tb3+ 5D4-7FJ (J = 6 - 3) transitions due to an energy transfer from WO4(2-) groups to Tb3+.

Bundle-shaped cyclodextrin-Tb nano-supramolecular assembly mediated by C60: intramolecular energy transfer.

A bundle-shaped nano-supramolecular assembly possessing numerous luminescent cyclodextrin-Tb polyads and photosensitizing C(60) units has been constructed through the end-to-end inclusion complexation of cyclodextrin cavities with C(60)s, and its properties have been comprehensively characterized. Further investigations on the luminescence properties of the cyclodextrin-Tb polyad and the bundle-shaped assembly demonstrate that a pyridine --> Tb --> C(60) intramolecular energy transfer process is operative when a solution of the assembly is exposed to UV light.

Thermoluminescence of terbium sensitised by samarium in CaF2.

Thermoluminescence (TL) in sintered CaF2 doped with Tb4O7 has been studied for UV and X-ray irradiation. Three TL glow peaks for the Tb4O7 doped sample appeared in the temperature regions of about (1) 347-353 K, (2) 378-383 K and (3) 453-458 K, when heated at a rate of 20 K min(-1) after UV or X-ray irradiation at room temperature. It has been found that the 378 K peak intensity of the samples co-doped with Tb4O7 and Sm2O3 became stronger when compared with those doped with only terbium or samarium ions, and the TL peaks of (1) 347-353 K and (3) 453-458 K were not observed. The intensity of the 378 K peak of the co-doped sample was 12.9 times that of the sample doped only with Tb4O7. From the TL spectra and the excitation and emission spectra of photoluminescence for the CaF2 doped activators, it is concluded that the TL of Tb3+ ions is sensitised by the existence of Sm3+ ions. The 378 K TL peak may also be suitable for UV radiation dosimetry.

Optically and thermally stimulated luminescence characteristics of MgO:Tb3+.

In this paper main optically stimulated luminescence (OSL) and thermoluminescence (TL) characteristics are presented of a newly synthesised material MgO doped with terbium (Tb) developed at the Institute of Nuclear Science, Vinca. A thermally stimulated emission spectrum showed the characteristic lines of Tb3+ in a wide range of wavelengths. The TL sensitivity of the main TL glow peak at 315 degrees C is 1.7 times higher than the TL of Al2O3:C. The highest OSL sensitivity was obtained under green lamp (500-570 nm) stimulation. The fast component in the OSL decay curve is 2.4 times faster than Al2O3:C. The OSL signal is linear with dose up to 10 Gy. The lower limit of detection was found to be 100 microGy. These first results show that the newly synthesised material has some promising properties for the application in radiation dosimetry.

Thermoluminescence response of K2YF5:Tb3+ crystals to photon radiation fields.

This investigation has been performed to test the feasibility of using K2YF5:Tb3+ crystals as thermoluminescence dosemeters (TLD). K2YF5 single crystals doped with 0.2, 10.0 and 50.0 at.% of trivalent optically active Tb3+ ions as well as K2TbF5 and undoped K2YF5 crystals have been synthesized under hydrothermal conditions. Polished crystal platelets with thickness of about 1 mm have been irradiated with X and gamma rays in order to study thermoluminescent (TL) sensitivity as well as dose and energy response in terms of the Tb3+ concentration in K2YF5. Within this concentration series, K2YF5 crystals doped with 10.0 at.% Tb3+ have been found to have maximum TL response due to a broad asymmetric TL glow peak at 269 degrees C with good linearity of dose response and reproducibility of dose measurements. After deconvolution, the main dosimetric peak has been revealed to be composed of two individual peaks, both with linear TL response behaviour, centered at 210 and 269 degrees C. As it has been proved, the linear TL signal coefficient for K2Y0.9Tb0.1F5 is almost 10 times greater than that for commercial TLD-100 (LiF:Mg,Ti), irradiated with a 137Cs gamma radiation source at the same conditions. The reported results indicate that K2YF5 crystals doped with Tb3+ have potential as promising materials for radiation dosemeters.

Sensitization of lanthanides by nonnatural amino acids.

The sensitization of Eu(III) and Tb(III) by ethylenediaminetetraaceticacid (EDTA)-derivatized tryptophan (Trp), 7-azatryptophan (7AW) and 5-hydroxytryptophan (5HW) has been examined. These Trp analogs were utilized in the present study because they can be incorporated into proteins in place of native Trp residues and because they absorb strongly beyond 305 nm (where Trp absorbance goes to zero), allowing selective excitation of such species in the presence of other Trp-containing proteins. All three indole derivatives were able to sensitize Tb(III) luminescence, with the relative sensitization being in the order Trp > 5HW > 7AW. On the other hand, only the 7AW-EDTA complex was able to sensitize Eu(III) luminescence, likely owing to a better spectral overlap between 7AW emission and Eu(III) absorbance. The sensitized emission of Tb(III) and Eu(II) displayed the expected long emission lifetimes at 545 nm [for Tb(III)] and 617 nm [for Eu(III)], indicating that long-lifetime lanthanide emission could be produced using nonnatural amino-acid donors. Thus, 7AW- and 5HW-sensitized lanthanide emissions should prove to be useful in biophysical studies, such as the use of fluorescence energy transfer to probe biomolecular interactions in vivo.

Thermoluminescence in sintered CaF2:Tb.

In order to observe and estimate the dose of ultraviolet (UV) radiation, the thermoluminescence (TL) of sintered CaF2 doped with Tb4O7 and Sm2O3 was studied. A several kind of lanthanides elements are doped in pure CaF2 powder crystals and properties of the TL to UV radiation were observed. The TL intensity from CaF2:Tb was the highest among the samples doped other lanthanide elements. The TL emission may be due to the recombination reaction; Tb2+ + hole-->Tb3+*-->Tb3+ + hv. The TL peaks are observed at about 353 K, 378 K and 458 K. It was found that the 378 K TL peak intensity of CaF2:Tb became strong by addition of Sm2O3. The 378 K TL peak may also be suitable for use as a dosimeter.

Measurement of the response of Gd2O2S:Tb phosphor to 6 MV x-rays.

The phosphor GdO2S:Tb is widely used in camera-based electronic portal imaging devices (EPIDs). There is considerable interest in the application of EPIDs to dosimetry and the verification of intensity modulated radiation therapy produced by dynamic multileaf collimation (DMLC). This paper presents direct measurement of Gd2O2S:Tb phosphor luminescence under 6 MV x-ray irradiation from a linear accelerator using a photomultiplier tube. The luminescence following each radiation pulse (3 micros duration) was observed to decay with a dominant lifetime of 558 micros. Using a specialized electrometer, the temporal variation of the optical signal has been compared with the dose rate incident on the phosphor measured using a semiconductor diode detector. Under dose rates typical of those used in the clinic (1.2 Gy min(-1) to the phosphor), measurements at beam-start confirmed that the optical signal is linear with dose per radiation pulse. Measurements at beam termination following phosphor doses up to 4.4 Gy showed no residual signal associated with long-lived luminescence (afterglow) from the phosphor above the noise level of the optical signal (0.17% standard deviation). This measurement demonstrates that afterglow from Gd2O2S:Tb is not of significance for its application to DMLC verification. Additionally, it was confirmed that the accelerator pulse repetition frequency has no effect on the optical signal from the phosphor in the range 25-400 Hz.