Terbium Ions Research Articles

Ionic nanosphere as a novel sensitizer for luminescence from terbium(III) ion hybridized by facile ion-exchange process

Abstract Luminescence from terbium(III) species is typically weak due to its low absorption coefficient and slow radiative process despite its advantageous color purity. Hybridizing with a photosensitizer(s) is one of the most popular strategies to obtain intense luminescence from terbium(III) species. We have developed a novel photosensitizing system in which terbium(III) ion is hybridized with the ionic nanosphere, a class of spherical ion-exchange resins with a diameter of <300 nm. Terbium(III)-doped ionic nanospheres successfully exhibited obvious green luminescence upon the photoexcitation of the nanosphere at 260 nm. The terbium(III)–nanosphere hybrids can be prepared by a simple methodology, and sample conditions are controllable facilely.

Opal photonic crystal double‐network hydrogel for visual detection through structural color and fluorescent responsiveness

AbstractPhotonic crystal hydrogels are widely used in the field of visual detection, based on the response of the structural color to external stimulus, such as pH, temperature, near‐infrared light, and so on. Here, we develop an opal photonic crystal hydrogel by combining polystyrene (PS) photonic crystals with a fluorescent double‐network hydrogel and focus on both its visual detection function and mechanical property. The opal hydrogel is composed of nanocomposite hydrogel as the first network and ionic crosslinked hydrogel as the second network. The introduction of PS photonic crystals and terbium ions endows the opal hydrogel distinctive structural colors and fluorescence, respectively. Because of volume changes, the structural color of the opal hydrogel selectively responses to metal ions and organic solvents. Attributing to the ion exchange interaction, the opal hydrogel exhibits fluorescent responses to various metal ions. Combining the responsiveness of structural color and fluorescence, a visual dual‐detection mode is set up, with better detection sensitivity and selectivity. Moreover, the characteristics of nanocomposite and double‐network crosslinking ensure the opal hydrogel enough mechanical properties to undergo cycle visual detection. Consequently, the fabricated opal hydrogel is promising for use in visual detection to multiple substances in single‐ or dual‐detection mode.

Design of Biologically Active Macromolecular Ligands and Their Luminescent Complexes with Terbium Ions

Design of Biologically Active Macromolecular Ligands and Their Luminescent Complexes with Terbium Ions

Tridentate Nitrogen Ligand as a Tool for the Construction of Well-Defined Rare Earth Trichloride Complexes.

LnCl3(THF)3 (Ln = Y, La ÷ Nd, Sm ÷ Lu) readily react with the tridentate 1,3,5-trimethyl-1,3,5-triazacyclohexane (Me3tach) ligand to form mono- or binuclear lanthanide trichloride complexes, depending on the stoichiometry of the reaction and the ionic radius of the metal: mononuclear pseudosandwich [LnCl3(Me3tach)2], (Ln = Y, La ÷ Ho) or binuclear complexes [Ln2Cl6(Me3tach)3], or [LnCl3(Me3tach)(THF)]2 (Ln = Sm, Tb). Detailed analysis of the NMR data of [LnCl3(Me3tach)2] complexes with paramagnetic lanthanide ions showed that their structures remained unchanged in the toluene solution. A series of isomorphous complexes [LnCl3(Me3tach)(Py)2] (Ln = La, Sm, Tb, Er, Lu; Py = pyridine) have been obtained by the recrystallization of either mononuclear or binuclear complexes from pyridine. Complexes of terbium and europium ions with the Me3tach ligand exhibit relatively high quantum yields of metal-centered luminescence (0.39 and 0.32, respectively).

A ternary nucleotide-lanthanide coordination nanoprobe for ratiometric fluorescence detection of ciprofloxacin.

Ciprofloxacin (CIP) is a widely used broad-spectrum antibiotic and has been associated with various side effects, making its accurate detection crucial for patient safety, drug quality compliance, and environmental and food safety. This study presents the development of a ternary nucleotide-lanthanide coordination nanoprobe, GMP-Tb-BDC (GMP: guanosine 5'-monophosphate, BDC: 2-amino-1,4-benzenedicarboxylic acid), for the sensitive and ratiometric detection of CIP. The GMP-Tb-BDC nanoprobe was constructed by incorporating the blue-emissive ligand BDC into the Tb/GMP coordination polymers. Upon the addition of CIP, the fluorescence of terbium ion (Tb3+ ) was significantly enhanced due to the coordination and fluorescence sensitization properties of CIP, while the emission of the BDC ligand remained unchanged. The nanoprobe demonstrated good linearity in the concentration range of 0-10 μM CIP. By leveraging mobile phone software to analyze the color signals, rapid on-site analysis of CIP was achieved. Furthermore, the nanoprobe exhibited accurate analysis of CIP in actual drug and milk samples. This study showcases the potential of the GMP-Tb-BDC nanoprobe for practical applications in CIP detection.

Immobilization of europium and terbium ions with tunable ratios on a dispersible two-dimensional metal-organic framework for ratiometric photoluminescence detection of D2O.

A two-dimensional zirconium-based metal-organic framework (2D Zr-MOF), ZrBTB (BTB = 1,3,5-tri(4-carboxyphenyl)benzene), is used as a platform to simultaneously immobilize terbium ions and europium ions with tunable ratios on its hexa-zirconium nodes by a post-synthetic modification. The crystallinity, morphology, porosity and photoluminescence (PL) properties of the obtained 2D Zr-MOFs with various europium-to-terbium ratios are investigated. With the energy transfer from the excited BTB linker to the installed terbium ions and the energy transfer from terbium ions to europium ions, a low loading of immobilized europium ions and a high loading of surrounding terbium ions in the 2D Zr-MOF result in the optimal PL emission intensities of europium; this phenomenon is not observable for the physical mixture of both terbium-installed ZrBTB and europium-installed ZrBTB. The role of installed terbium ions as efficient mediators for the energy transfer from the excited BTB linker to the installed europium ion is confirmed by quantifying PL quantum yields. As a demonstration, these materials with modulable PL characteristics are applied for the ratiometric detection of D2O in water, with the use of the stable emission from the BTB linker as the reference. With the strong emission of immobilized europium ions and the good dispersity in aqueous solutions, the optimal bimetal-installed ZrBTB, Eu-Tb-ZrBTB(1 : 10), can achieve the sensing performance outperforming those of the terbium-installed ZrBTB, europium-installed ZrBTB and the physical mixture of both.

Intensity and lifetime ratiometric luminescent thermometer based on a Tb(III) coordination polymer.

A three-dimensional terbium(III) coordination polymer of formula [Tb(bttb)0.5(2,5-pzdc)0.5]n (1) [H4bttb = 1,2,4,5-tetrakis(4'-carboxyphenyl)benzene and H2-2,5-pzdc = 2,5-pyrazinedicarboxylic acid] was obtained under hydrothermal conditions. The bttb4- tetraanion in 1 adopts the bridging and chelating-bridging pseudo-oxo coordination modes while the 2,5-pzdc2- dianion exhibits a rather unusual bis-bidentate bridging pseudo-oxo coordination mode, both ligands being responsible for the stiffness of the resulting 3D structure. Solid-state photoluminescent measurements illustrate that 1 exhibits remarkable green luminescence emission, the most intense band occurring in the region of 550 nm (5D4 → 7F5) with lifetimes at the millisecond scale. Thermometric performances of 1 reveal a maximum relative sensitivity (Sm) of 0.76% K-1 at 295 K (δT = 0.05 K), constituting a TbIII ratiometric solid luminescent thermometer over the physiological temperature range. Variable-temperature static (dc) magnetic susceptibility measurements for 1 in the temperature range 2.0-300 K show the expected behavior for the depopulation of the splitted mJ levels of the 7F7 ground state of the magnetically anisotropic terbium(III) ion plus a weak antiferromagnetic interaction through the carboxylate bridges. No significant out-of-phase magnetic susceptibility signals were observed for 1 in the temperature range 2.0-10.0 K, either in the absence or presence of a static dc magnetic field.

Rare earth element extraction from geothermal brine using hybrid capacitive-deionisation process

Rare Earth Elements (REE) in geothermal brine include pollutants such as dissolved Lanthanum, Cerium, Praseodymium, Neodymium, Promethium, Samarium, Europium, Gadolinium, Terbium, Dysprosium, Holmium, Erbium, Thulium, Ytterbium, lithium, and other ions. These REEs in geothermal brine, also popularly known as “Vitamins of the modern industry”, are vital for industries such as new energy vehicles, wind turbines, radar systems, laser crystals, etc., and harmful for agriculture and drinking purposes. Hence, identifying, quantifying, and extracting these REEs are essential and economical for a geothermal plant. The present study systematically investigates identifying and quantifying the REE and other essential ions in geothermal brine sources from Gujarat regions. For the extraction of REE from geothermal brine, geothermal brine treatment systems and their integration with automation control are designed in the present work. The proposed system filters geothermal brine and extracts REE through a hybrid filtration setup using capacitive deionization. Solar photovoltaic Water Filtration uses a hybrid Capacitive De-Ionization (CDI) treatment-based prototype to purify water and extract REE. The CDI method is an emerging technology in the desalination systems. It has far greater leverage over other desalination methods such as electrodialysis. The proposed design allows the simultaneous removal of various dissolved organic and inorganic contaminants in geothermal brine.

Construction of dual-mode photochromic fluorescence switching system based on water-soluble rare earth phosphates and carboxyl-containing diarylethene

Photochromic fluorescent switches have been attracting great research interest owing to their optical color and fluorescence can be reversibly modulated by light stimulation. An efficient way to construct photochromic fluorescence switching system is to integrate photochromic molecule with an energy level-matching fluorophore by non-covalent assembly. In this paper, we reported the design of a water-soluble photochromic fluorescent switch (OF–CO2H@Ce6Tb4·P) with dual signal changes (optical color change and fluorescence ON/OFF) by combining Ce, Tb co-doped phosphate hybrid (Ce6Tb4·P) and diarylethene containing carboxyl groups (OF–CO2H) via hydrogen bonding. Ce6Tb4·P showed the typical green fluorescence of terbium ions due to the sensitization effect of cerium ions. OF-CO2H can undergo reversible photoisomerization reaction, accompanied by changes in optical color (colorless to pink) and UV–visible absorption. Moreover, controlling the photoisomerization of OF-CO2H can regulates the spectral overlap between its absorption and Ce6Tb4·P emission, thus achieving reversible modulation of the optical color and fluorescence of OF-CO2H@Ce6Tb4·P. The demonstrations of photocontrolled dual-mode signaling in photoswitchable patterning shows that OF-CO2H@Ce6Tb4·P is suited for surface-involved photocontrolled applications such as advanced optical anti-counterfeiting and information storage.

Lasing properties, Judd-Ofelt and band gap investigation of cool green emanating Tb3+ complexes for solid and solution state luminescence

Optical and photophysical characteristics of six green emanating terbium complexes which have been prepared by eco-efficient solvent assisted grinding process. The prepared complexes display bright green luminescence with a prominent peak at 548 nm accredited to 5D4 → 7F5 transition of terbium ions, as examined by PL emission spectra monitored at 355 nm excitation wavelength. Spectroscopic investigation of these synthesised complexes was explored. Photometric features such as CIE coordinate, CCT and %CP asserted their green luminescence and are found in agreement with brilliant green light. Lasing properties, optoelectronic and thermal analysis of terbium complexes were performed. To determine the coordination environment around the metal ion, JO parameter (Ω2, Ω4, Ω6) and intensity ratio were also determined. The research offers a glowing cool green emitting constituent for the manufacturing of OLEDs and innovative optoelectronic devices. Antioxidant and antimicrobial properties were also examined. Computational studied of complexes were carried out successfully.

Nonlinear refraction in high terbium content borogermanate glass bulk and fiber

High terbium content glasses have stood out in technological areas due to their simultaneous ability of magnetization and transparency in the visible spectrum. Such magneto-optical glasses are relevant for several optical devices, including optical modulators, sensors, and isolators. While terbium ions are responsible for magnetic response, glass formers, and modifiers provide a branch of desirable mechanical, chemical, and optical properties, which can further be tailored by compositional manipulation. Determination of Verdet constant is usual in magneto-optical glass, however, little attention has been devoted to the determination of the optical properties, moreover the nonlinear ones. Herein, we investigate the nonlinear index of refraction (n2) of a novel magneto-optical glass shaped in bulk and optical fibers. Although the fabrication of fibers with high terbium content is challenging, the usage of optical fibers is important to improve signal that arises from magneto-optical and Kerr effects, since both depend on light propagation path. Bulk and optical fiber of 96(60GeO2-25B2O3–4Al2O3–10Na2O–1PbO) – 4Tb4O7 (mol%) glass were characterized by Z-scan and D-scan techniques, respectively, using femtosecond laser pulses. It was obtained the n2 spectrum in the range of 550–1200 nm for the former, which was modeled based on BGO model, revealing the role of oxygen ions for the optical nonlinearity. The optical fiber fabrication process does not compromise the n2 value, remaining n2=(5±2)×10−20m2/W at 790 nm according to D-scan measurements, which is equivalent to values determined by Z-scan, i.e. (6±2)×10−20m2/W. Additionally, the chemical states of the various elemental components of GBANP-4Tb glasses were investigated by X-ray photoelectron spectroscopy (XPS). The analysis of the Ge 3d and Tb 4f photoelectron spectra of the GBANP-4Tb glasses revealed the presence of Ge4+, Tb3+ and Tb4+ oxidation states. These results are relevant to expand the knowledge on magneto-optical materials, moreover regarding their optical response in the femtosecond regime, broadening its application in ultrafast magneto-optical devices.

Nanoobjects for the Luminescence Determination of Fluoroquinolones

Fluoroquinolones are the most successful antibiotics, which also show antiviral and antitumor activity. The widespread use of fluoroquinolones in medicine, pharmaceutical chemistry, veterinary medicine and in animal, poultry, and fish feeds requires continuous improvement of methods for their determination in various samples. Sensitized fluorescence based on resonance electronic excitation energy transfer (RET) during the formation of chelates with terbium and europium ions is a promising and highly sensitive method for the determination of fluoroquinolones. This review analyzes the use of two types of nanoobjects—liquid micellar nanosystems and quantum dots based on the nanoparticles of silver, gold, and semiconductors and carbon, magnetic, and other nanomaterials—for increasing the efficiency of energy transfer and the sensitivity of the determination of fluoroquinolones in various samples. The terminology used in the inductive-resonance and exchange-resonance mechanisms of energy transfer is considered, and the fundamental difference in RET between liquid and solid types of nanoobjects is shown. Linear dynamic ranges of determined concentrations, limits of detection, and examples of practical application of sensitized fluorescence to the determination of fluoroquinolones in real samples with the use of nanoparticles and micellar nanosystems are tabulated.

Nanoobjects for the Luminescence Determination of Fluoroquinolones

Fluoroquinolones are the most successful antibiotics, which also show antiviral and antitumor activity. The widespread use of fluoroquinolones in medicine, pharmaceutical chemistry, veterinary medicine and in animal, poultry, and fish feeds requires continuous improvement of methods for their determination in various samples. Sensitized fluorescence based on resonance electronic excitation energy transfer (RET) during the formation of chelates with terbium and europium ions is a promising and highly sensitive method for the determination of fluoroquinolones. This review analyzes the use of two types of nanoobjects—liquid micellar nanosystems and quantum dots based on the nanoparticles of silver, gold, and semiconductors and carbon, magnetic, and other nanomaterials—for increasing the efficiency of energy transfer and the sensitivity of the determination of fluoroquinolones in various samples. The terminology used in the inductive-resonance and exchange-resonance mechanisms of energy transfer is considered, and the fundamental difference in RET between liquid and solid types of nanoobjects is shown. Linear dynamic ranges of determined concentrations, limits of detection, and examples of practical application of sensitized fluorescence to the determination of fluoroquinolones in real samples with the use of nanoparticles and micellar nanosystems are tabulated.

Effect of Gadolinium Oxide and Gadolinium Fluoride in Borophosphate Glasses Doped with Tb2O3 Content

The melt-quenching process synthesized gadolinium oxide and fluoride in borophosphate glasses doped with terbium ions (Tb3+). The effect of fluoride compounds and their impacts on physical, optical, and luminescent properties have been investigated. The glasses absorbed near-infrared, visible light, and ultraviolet photons. The bright green emission circa 542 nm via the 5D4 → 7F5 radiative state of Tb3+ originated. Depending on the excitation, there are several sorts of ultraviolet, visible light, and X-ray. The values of decay time are in the order of milliseconds (ms). The Gd3+-Tb3+ energy transfer is vital in green emission under 275 nm excitation. According to the results obtained in this work, the developed glasses can be suitable candidates for green emission medium.

Tb3+-nucleic acid probe-based label-free and rapid detection of mercury pollution in food

Mercury is a threatening pollutant in food, herein, we developed a Tb3+-nucleic acid probe-based label-free assay for mix-and-read, rapid detection of mercury pollution. The assay utilized the feature of light-up fluorescence of terbium ions (Tb3+) via binding with single-strand DNA. Mercury ion, Hg2+ induced thymine (T)-rich DNA strand to form a double-strand structure (T-Hg2+-T), thus leading to fluorescence reduction. Based on the principle, Hg2+ can be quantified based on the fluorescence of Tb3+, the limit of detection was 0.0689 μmol/L and the linear range was 0.16 μmol/L. Due to the specificity of T-Hg2+-T artificial base pair, the assay could distinguish Hg2+ from other metal ions. The recovery rate was ranged in 98.71 %101.34 % for detecting mercury pollution in three food samples. The assay is low-cost, separation-free and mix-to-read, thus was a competitive tool for detection of mercury pollution to ensure food safety.

Polarization Processes in Nafion Composite Membranes Doped with Rare-Earth Metals.

Dielectric spectroscopy (frequency range f = 100…107 Hz and temperatures T = 293…403 K (accuracy 0.5 K), measuring voltage applied to the sample was 1.0 V) was used to study composite materials based on perfluorosulfonic membranes with inclusions of rare-earth elements, in particular, europium (III) and terbium (III) chlorides. The dispersion of the permittivity and the presence of maxima, corresponding to losses, were revealed, which indicates that relaxation processes of various natures were present. The membrane layers under investigation are characterized by relaxation parameters that correspond to a symmetrical distribution of relaxers over relaxation times. The spectrum of relaxers changed when terbium and europium metal impurities were introduced into the polymer matrix. The investigation of these polymer systems demonstrated a power-law dependence of the specific conductivity on frequency. A decrease in the exponent with increasing temperature indicates the existence of a traditional hopping mechanism for charge transfer. The observed changes in the dielectric permittivity and specific conductivity are due to a change in the nature of polarization processes because of the strong interaction of metal (terbium and europium) ions with the polymer matrix of Nafion.

Terbium doping and energy level modification of zirconium organic frameworks as probes for the improved determination of histamine and visual inspection of food freshness

Food safety is a common concern among people, and the development of high-performance food freshness detection technology is crucial, but is still highly challenging. Fluorescent sensing based on metal organic frameworks is a promising technology to tackle this issue. In this work, three UiO-66 type Zirconium organic frameworks (ZrOFs) which are functionalized with varying numbers of hydroxyl groups to alter the energy levels, and partial replacement of Zirconium(IV) by Terbium(III) ions to introduce additional emitting centers, were explored as probes for the sensing of Histamine (His). With one hydroxyl group introduced, UiO-66-OH@Tb can be developed as ratiometric fluorescent probe with improved sensing performance, showing a wide detection range of 0 to 120 mg/L, and a low detection limit of 0.13 mg/L. UiO-66-OH@Tb can also be fabricated into composite film to function as visual sensing material of His. This work can provide instructions for the development of other fluorescent sensors.

Magnetic-encoded fluorescent nanospheres-based competitive immunoassay for near-simultaneous detection of four mycotoxins in wheat

Simultaneous detection of mycotoxins is important for food safety. In this study, a magnetic-encoded fluorescent nanosphere-based competitive immunosensor (cFMEIS) with 2×2 array was first developed for simultaneous detection of aflatoxin B1 (AFB1), ochratoxin (OTA), deoxynivalenol (DON), and zearalenone (ZEN) in wheat. Specifically, magnetic nanoparticles with strong and weak responses were conjugated with mycotoxin antigens as capture probes. Fluorescent nanoparticles doped with europium ion (Eu3+) and terbium ion (Tb3+) with red and green emission were coupled with mycotoxin antibodies as signal probes. Using a magnetic field, immune complexes were sequentially separated in a complex system and fluorescently detected. The detection limits of AFB1, DON, OTA, and ZEN were 0.032, 0.141, 0.097, and 0.376 μg/kg, respectively. The recoveries in the certified reference material of wheat flour ranged from 81.6 to 120.0 %. Owing to its high accuracy, selectivity, and sensitivity, the cFMEIS shows great promise as an efficient and sensitive multitarget sensor for mycotoxins.

Energy transfer and photoluminescence properties of CaYGaO4:Bi3+,Tb3+ phosphors

Trivalent bismuth and trivalent terbium ions doped CaYGaO4 were prepared. The crystal structure, phase purity, photoluminescence, decay curves, and emission spectra under various temperatures were investigated. The six-coordinate Ca2+ and Y3+ ions are occupied by Bi3+ ions, while Tb3+ ions take up the six-coordinate Y3+ ions in the CaYGaO4:Bi3+,Tb3+ phosphor. The emissions of trivalent bismuth (3P1 → 1S0) and trivalent terbium ions (5D4 → 7F5) excited by 320 nm were observed. The analysis of spectra and decay curves demonstrated that Bi3+ could transfer energy to Tb3+ via electric dipole-quadrupole interaction. By altering the concentration of trivalent terbium ions, the emitting color of phosphor was tuned from blue to green. The temperature sensing property of CaYGaO4:Bi3+,Tb3+ was described, and its relative sensitivity at 303 K achieves a maximum of 0.61% K−1. According to the results, CaYGaO4:Bi3+,Tb3+ is a potential material for color tunable emission and temperature sensing.

Effects of terbium ions on the structural, morphological and optical properties of zinc selenide thin films prepared by photo-assisted chemical bath method

This study presents undoped and terbium doped ZnSe thin films deposited at different terbium III (Tb3+) ion concentrations using Photo-assisted chemical bath technique. The samples were characterized using glancing incidence X-ray diffraction (GIXRD), Raman spectroscopy, ultraviolet-visible spectroscopy, and photoluminescence (PL) spectroscopy, field emission scanning electron microscope, Atomic force microscopy and energy dispersive X-ray spectroscopy. The GIXRD and Raman peaks intensities, surface roughness and energy band gap increased with increasing Tb3+ ions concentration up to 0.8% and decreased thereafter. This behavior, which is equally observed in the PL emission, is ascribed to concentration quenching due to the presence of natural defect in the host material. Three PL emission peaks all associated with the defects were observed at 535, 672 and 743 nm. The thin films morphology transformed from flakes to spherical grains with increased Tb3+ ions concentration and the presence of the expected elements was confirmed. The deposited films have potential applications in light emitting devices.