Terbium Ions Research Articles

An Ultrasensitive Self‐Calibrating Terbium Metal Organic Framework for the Detection of Amphotericin B

ABSTRACTWe successfully synthesized a 3D porous lanthanide metal–organic framework, [Tb (obdb)][Tb1/3(H2O)7/3]·NMP (Tb‐MOF) with hydrated terbium ions in the pores by solvothermal method using 4′,4″′‐oxybis[1,1′‐biphenyl]‐3,5‐dicarboxylic acid (H4obdb) as ligand. It is worth mentioning that Tb‐MOF exhibits excellent performance in structural stability and fluorescence response. Even after soaking in various solvents and pH solutions for 3 months, Tb‐MOF can maintain its structural integrity and excellent stability. The fluorescence spectra show that Tb‐MOF not only exhibits the luminescence of the ligand centered at 368 nm (IL), but also emits the characteristic emissions of the metal terbium, among which the luminescence at 542 nm is the strongest. In the detection of antibiotic amphotericin B (AB), Tb‐MOF showed significant detection efficiency. Upon increasing the concentration of AB, the fluorescence intensity at 542 nm gradually decreased, whereas the fluorescence at 368 nm decreased rapidly. The I542/IL value showed a very high linear correlation with AB concentration, with the slope reaching 1.29 × 108 M−1 (0–100 μM). In the field of fluorescent sensors for AB detection, Tb‐MOF is notable not only for its impressively low LOD (limt of detection) of 0.072 nM but also for pioneering the application of a self‐calibrating ratio‐based detection method. To better elucidate this fluorescence sensing phenomenon, we also conducted a detailed discussion of the sensing mechanism for AB.

A promising green fluorimetric approach for analysis of edoxaban in real human plasma using green carbon dots decorated with terbium ions

A promising green fluorimetric approach for analysis of edoxaban in real human plasma using green carbon dots decorated with terbium ions

Strategic enhancement of collagen detection using lanthanide-functionalized collagen targeted peptides

Monitoring collagen denaturation is crucial for diagnosing collagen-related diseases such as tumors and fibrosis. Herein, we have developed specific probes to detect denatured collagen (d-Col) and collagen I (Col I), utilizing peptide probes with sequences (GOP)10 and HVWMQAP, targeting at d-Col and Col I, respectively. These peptides were conjugated with 1,10-phenanthroline-5-carboxylic Acid (Phen), forming Phen-Ahx-(GOP)10 and Phen-Ahx-HVWMQAP. Phen acts as both an antenna sensitizer and a chelator, coordinating with Terbium (III) and Europium (III) ions via its nitrogen atom, facilitating fluorescent emission in green and red, respectively. The investigation demonstrated that Tb3+ interacts with three (GOP)10 peptide units through Phen, while Eu3+ connects with four units of Ahx-HVWMQAP peptides. Additionally, it is important to note that the structure of the peptides remains unchanged after chelating with the lanthanide ions, maintaining their integrity throughout the process. These probes have effectively demonstrated their ability to bind to specific collagen types with selectivity, enabling accurate identification of their presence. The excellent binding of these probes is due to the branched structure of the formed lanthanide-peptide complexes. A dose-dependent linear association was observed in the binding of Eu-[Phen-Ahx-HVWMQAP]4 to Col I, with concentration levels ranging from 0.5 to 100 μM and a minimal detectable concentration of 0.113 μM. We anticipate that our developed probes will improve understanding of collagen remodeling and provide opportunities for the diagnosis of collagen-associated diseases.

Impact of the host lattice on crystallographic, Raman, optical, and luminescent properties on the terbium ion

AbstractA comparative study of the Gd2O3:Tb and Y2O3:Tb nanoparticles (NPs) was presented to examine the influence of the host lattices on the crystallographic phase, surface characteristics, optical properties, Raman effect, and photoluminescence properties. Cubic shapes Gd2O3:Tb and Y2O3:Tb NPs with an estimated crystalline size of 17 and 11 nm were recorded from the X‐ray diffraction pattern, respectively. Comparative absorption spectra of both oxides NPs were presented to examine the dispersibility, colloidal stability, and optical behavior of the NPs. Energy bandgap values were estimated to monitor the optical characteristics of the metal oxides in the UV/Vis region. Fourier transform infrared was recorded to confirm the surface‐attached water and organic moieties. The Raman spectra of metal oxides were recorded to examine the symmetrical dis‐order and polarizability of the vibrational bands. The ionic radius of the atoms distorts the bond structure resulting in it greatly influenced the vibrational bands of the materials. The emission spectra certified the effective doping of the luminescent Tb3+‐ion in the metal oxide host lattices. Raman spectra and emission spectra validated the crystal symmetry imperfections; subsequently, the efficiency of the Raman active modes and emission transitions was greatly influenced. In a comparative analysis, Y2O3:Tb NPs exhibited higher luminescence intensity in comparison with the Gd2O3:Tb NPs.

A New approach for simultaneous detection and photocatalytic degradation of imidacloprid and dinotefuran in water using terbium-based fluorometry and mixed-phase TiO2

This study explores a novel method for detecting neonicotinoid insecticides, imidacloprid (IMD) and dinotefuran (DNT), in water using terbium (Tb3+) ions photo probe. The optimal excitation and emission wavelengths for Tb3+ luminescence were identified at 310 nm and 545 nm, respectively. The influence of pH and solvent on Tb-complex fluorescence was investigated. Results indicate a significant enhancement of luminescence intensity at pH 6 for IMD in DMF and pH 7.0 for DNT in DMSO. The fluorescence intensity exhibited a linear relationship with IMD and DNT concentrations ranging from 0.1 to 20 µg/mL (R2 > 0.99). Limits of quantitation (LOQ) were determined as 0.1 µg/mL for IMD and 0.05 µg/mL for DNT. This newly developed photo probe demonstrates the potential for monitoring photolysis and photocatalytic degradation of these neonicotinoids using TiO2 as a catalyst under controlled photoreactor conditions. The method offers a promising alternative for rapidly and sensitively detecting these prevalent insecticides in water samples.

Temperature Changes in Luminescence of Mixed Complexes of Terbium and Samarium with Organic Ligands Based on 2,2-bipyridyldicarboxamides

Solutions in acetonitrile of three mixed complexes of rare earth elements (terbium and samarium) with organic ligands with various pyridine substituents were studied in this work. The ratios of ligands and metals in the resulting complexes were determined, and the stability constants of samarium complexes were calculated using the spectrophotometric titration method. Measurements of absorption, emission and excitation spectra of luminescence, luminescence kinetics of solutions of mixed complexes of rare earth elements with an excess of metal relative to the ligand were carried out at various temperatures in the range 298–328 K. An increase of luminescence intensity of a samarium ion in complex upon heating has been discovered for the first time. The dependences of the luminescence quantum yield and lifetime of mixed complexes on temperature were obtained. A thermometric parameter — the ratio of the integral luminescence intensities of samarium and terbium ions — was proposed, and the temperature sensitivity coefficient of this parameter was determined for different complexes.

The interplay between structural features and the efficiency of the energy transfer process in terbium complexes with triarylcyclopentadienyl ligands

Terbium and gadolinium complexes with triarylcyclopentadienyl ligands having electron-donating methoxy substituents in the ortho- (CpPh2Ar−o) and para- (CpPh2Ar−p) positions of one of the phenyl rings have been synthesized. Different structural types, including tetranuclear [{CpPh2Ar−oTb (THF)}2 (μ2-Cl)2(μ3-Cl)3K (THF)]2 (Tb1), [{CpPh2Ar−oTb}2 (μ2-Cl)2 (μ3-Cl)3K]2 (Tb3), [{(CpPh2Ar−oTb)2 (μ2-Cl)3}2 (μ2-Cl)2] (Tb5), [{CpPh2Ar−pTb (THF)}2 (μ2-Cl)2 (μ3-Cl)3K (THF)]2 (Tb6), binuclear [{CpPh2Ar−oTb (THF)Cl}2 (μ2-Cl)2] (Tb4), [{CpPh2Ar−pTb (THF)}2 (μ2-Cl)2 (μ3-Cl)3K (THF)]2 (Tb7), [CpPh2Ar−p2Tb (μ2-Cl) (μ3-Cl)K]2 (Tb8) and mononuclear [CpPh2Ar−o2TbCl] (Tb2) complexes have been obtained and confirmed by single crystal X-ray diffraction analysis. All designed terbium complexes exhibit high quantum yields of the photoluminescence (up to 65 %). The introduction of a methoxy group into one of the phenyl rings of the triarylcyclopentadienyl ligand leads to a more than twofold increase in the quantum yield of the terbium ion luminescence. The estimated values of radiative rate krad of the terbium ion vary in the range of 0.23–0.69 ms. The presence of the methoxy group as well as the mutual disposition of the phenyl rings promotes the appearance of an intraligand charge transfer states involved in the energy transfer process. Due to a lowering of the energy of the interconfigurational 4f −5d transitions caused by the relatively strong crystal field of the Cp ligand in bis(cyclopentadienyl) terbium complexes, the quantum yield of the photoluminescence is high at the short lifetimes of the 5D4 level of the terbium ion.

Spectroscopic analysis of La2(WO4)3:Tb3+ phosphor and the delayed concentration quenching of 5D4 →7FJ emission

Trivalent terbium ion doped lanthanum tungstate (La2-xTbx(WO4)3; x = 0.6,1.0,1.4) and terbium tungstate (Tb2(WO4)3) phosphors were successfully synthesized via optimized microwave-assisted co-precipitation technique. The phase purity and crystallinity of the prepared samples were confirmed using the powder XRD technique. The photoluminescence studies revealed a quenching-free emission up to 70 % of Tb3+ doping concentration, even though the emission intensity slightly decreases under host excitation since it becomes less relevant at higher doping concentrations. The experimental and calculated oscillator strengths were evaluated using absorption data and further used to quantify the Judd - Ofelt (JO) intensity parameters, which appeared in a trend of Ω2>Ω4>Ω6 for all samples. As a theoretical approach to assure the excellency of the tungstate host, the radiative parameters were calculated from the emission data using the JO analysis technique. The dominance in the values of stimulated emission cross section and gain bandwidth corresponding to 5D4→7F5 transition of Tb3+ ion of lanthanum tungstate proclaims it as an excellent green phosphor. Hence, the less susceptibility of the tungstate host towards concentration quenching is confirmed in the present work.

A Terbium Ion-Based Dual-Ligand Fluorescent Probe for Highly Selective and Sensitive Detection of Cu2+ Ions.

In this study, a fluorescent probe (GMP-Tb-SSA) utilizing lanthanide coordination polymer nanoparticles, GMP-Tb, as a sensing platform, and 5-sulfosalicylic acid (SSA) as a cofactor ligand was proposed for the detection of copper ions (Cu2+). GMP-Tb was synthesized by the self-assembly of guanine monophosphate (GMP) and terbium ion (Tb3+), and SSA was introduced as a sensitizer into the GMP-Tb network. Cu2+ could efficiently inhibit the electron transfer from the ligand GMP to the central ion, Tb3+, leading to a significant quench of fluorescence of Tb3+. The method is highly selective with a linear range of 0 to 21 µM and a detection limit of 300 nM. It is not interfered by metal ions, amino acids, and other species, and can be successfully applied to the detection of Cu2+ in real water samples.

Optical properties of multicomponent borate glasses doped with trivalent terbium ions

Optical properties of multicomponent borate glasses doped with trivalent terbium ions

Synthesis and fluorescence property of a new Tb-based metal-organic framework

A new 3D Terbium (III) metal-organic framework has been solvothermally synthesized by using terbium ion as the metal center and 1,1[Formula: see text],1[Formula: see text]-(2,4,6-trimethylphenyl-1,3,5-tri) trimethyl tritrium (4-carboxylpyridyl) tribromide (H3LBr3) as ligand. The molecular formula is [Tb(H3LBr3) (OH)2](NO3)●(DMAC)3. Compound crystallizes in the triclinic system, space group [Formula: see text], with [Formula: see text], [Formula: see text], [Formula: see text][Formula: see text]Å, [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text][Formula: see text]Å3, [Formula: see text], [Formula: see text], [Formula: see text][Formula: see text]g/cm3, [Formula: see text][Formula: see text]mm[Formula: see text], [Formula: see text], [Formula: see text] and [Formula: see text] for 7586 observed reflections ([Formula: see text] (I)). Meanwhile, the fluorescence property was also studied. The result shows that the synthesized Tb-MOF displays highly selective sensing of acetone.

Bimetallic metal-organic frameworks utilizing AIE for visual detection of glutathione and applications in information encryption

Glutathione (GSH) plays an important role in living organisms and is often added to food as a food additive, so it is of great importance to accurately and conveniently determine GSH in food. In this paper, a terbium and copper bimetallic metal-organic frameworks (Tbx/Cu1-x-BTC) was designed for the visualization and detection of GSH in food. Terbium ions in the Tbx/Cu1-x-BTC provide the background signal and act as an aggregation center. After reduction and aggregation-induced emission (AIE), GSH-modified copper nanoclusters (GSH-Cu NCs) enhance the red fluorescence and keep the green fluorescence unchanged. This results in a color shift of the system from green to orange. Combined with a smartphone, the RGB value of the system color was extracted to realize the visual detection of GSH. Due to the specificity of the reaction, Tbx/Cu1-x-BTC was able to specifically recognize GSH among GSH structural analogs with very good selectivity, anti-interference ability, sensitivity and accuracy. In addition, using the difference in color and excitation wavelength range between the probe and the reaction product, the probe was applied in the field of information encryption, which further expanded the application scenario of the probe. Therefore, this study provides new ideas for the detection of GSH in food and the application of fluorescence probes in the field of information encryption.

Ligand regulation strategy enhanced anodic electrochemiluminescence of copper nanoclusters for enrofloxacin trace determination

Copper nanoclusters (Cu NCs) have emerged as promising nano-emitters. However, their limited luminescence stability and emission intensity restrict their application in electrochemiluminescence (ECL). Herein, a ligand regulation strategy was developed to enhance the anodic ECL of Cu NCs. Specifically, we utilized ovalbumin (OVA), a naturally occurring protein, as a stabilizing ligand for the Cu NCs and introduced terbium ions into the ligand. This approach optimizes ECL performance by enhancing electron transfer efficiency and suppressing non-radiative relaxation. Additionally, we used the enhanced ECL nano-emitter as a signal probe and combined it with split aptamers to develop an analytical platform. This platform is designed for the detection of enrofloxacin (ENR) in food samples. The sensing platform incorporated a self-designed ENR test cell combined with 3D printing, ITO sputtering and screen-printing technologies, which greatly improved the reproducibility of the test results. Our study highlights the potential of this innovative detection method in the realm of food detection.

Micrometric patterning of a borogermanate glass containing terbium by thermal poling to manage luminescence and second order optical properties

Borogermanate glasses containing terbium ions are interesting materials due to their luminescent and magnetic properties. Terbium can present two different oxidation states and the thermal poling technique can be a pertinent way to modulate spatially the oxidation state of these ions. In this work, we demonstrate using a thermo-electrical imprinting process the transfer of micro scaled motifs on the surface of a borogermanate glass containing Tb3+ resulting in a micrometric structuring of the oxidation state of Tb3+/Tb4+ ions. A large change in absorption and luminescence optical properties is observed, arising from the distinct properties of trivalent and tetravalent terbium ions. Correlative micro luminescence, Raman and second harmonic generation measurements were carried out on the patterned poled glass surface. This has demonstrated an accurate concomitant modification of the glass structure accompanying large luminescence changes and the appearance of a second order optical response which could be attributed to a localized space charge implantation. These original results demonstrate how a simple electrical process allows managing multi optical properties but also paves the way to induce static electrical functionalities in a magnetic optical glassy system.

Weakly agglomerated NANO/MICRO-particles of Gd2O3:Tb3+: Structure, luminescence and thermometry

Gadolinium oxide nanostructures have been actively studied as multimodal materials for both technical applications and biomedical research. Doping of this oxide structure with a given concentration of chosen rare earth ions allows one to obtain predefined optical properties. Weakly agglomerated nanoscale and submicron Gd2O3:Tb3+ particles were synthesized by a modified Pechini method in a single chemical process. The nanoscale fraction was transferred into aqueous solution without the addition of surfactant. Zeta potential of this solution was found to be about −17 (±1) mV. The crystal structure of cubic gadolinium oxide is confirmed for the large and small size fraction. The optimal concentration of terbium ions, at which the highest luminescence is observed, was 1.2 at.%. The concentration quenching mechanism for Tb3+-doped Gd2O3 samples was determined as a dipole–quadrupole energy migration with subsequent quenching on impurities. The luminescence properties of sub-micron and nanoparticles, including lifetimes, were found to be almost identical. The effect of temperature on both steady-state and kinetic luminescent properties was studied. Gd2O3:Tb3+ phosphors were found to be promising as lifetime-based luminescent thermometers.

Detection of Fluorescently Labeled Carbohydrate-Deficient Transferrin, a Marker of Alcohol Dependence, in Dried Blood Spots

A fluorescence-based (HPLC-FLD) method was developed for the detection of carbohydrate-deficient transferrin (CDT), a marker of alcohol dependence, in dried blood spots (DBS). Dried blood spots were cut and immersed in hydrochloric acid to leach out proteins, labeled with terbium ions, and then sent to high-performance liquid chromatography coupled with a fluorescence detector for detection. The levels of CDT in the dried blood spot samples of 10 clinically alcohol-dependent individuals were in general agreement with the results of the assayed levels of CDT in serum samples from the same source. The method can effectively amplify the detection signal of micro samples with high sensitivity and specificity, and the sampling method is simple and convenient to ensure the accuracy of the results, which is suitable for the qualitative and quantitative analysis of CDT in clinical micro samples.

Effect of Na2O on Verdet constant of Tb-doped magneto-optical glass

The terbium (Tb) ions doped magneto-optical glasses have attracted significant attention due to their high Verdet constant and excellent optical properties. In the Tb ions doped glass, +3 and + 4 valence states of Tb ions coexisted. However, only the +3 valence is favorable for magneto-optical performance. This study proposed a strategy to increase the concentration of Tb3+ ions (CTb3+) in the glass. The high optical basicity Na2O is beneficial for enhancing the Verdet constant. The lower melting temperature suppresses the oxidation of the Tb3+ to Tb4+, leading to the increase of CTb3+. As a result, the Verdet constant at 650 nm was achieved as high as 78.6 rad/(T·m), representing a 42.8 % improvement compared to glasses melted at 1450 °C. This approach avoids glass crystallization at high concentrations of Tb doping and provides a new solution for preparing high-performance magneto-optical glasses.

Effects of Tb3+ on properties of luminescent calcium sulfate cement

Calcium sulfate powder materials containing terbium ions at 0, 1.0, or 2.0 mol.% were obtained. They are characterized by the presence of a CaSO4 × 0.5H2O phase, while Tb3+ is incorporated into the lattice at ≤1.0 mol.%. Specific surface area enlarged from 2.1 to 22.5 m2/g as crystallite size decreased from 68 to 31 nm. Thermal analysis showed that terbium slightly raises the temperature of CaSO4 × 2H2O-to-CaSO4 transition. Studies of solubility in SBF solution showed the presence of a calcium phosphate layer in terbium-containing cements on the 7th day. Luminescent properties were studied by excitation at 266 nm and 489 nm corresponding to absorption bands of the host and Tb3+ (7F6 - 5D4 absorption band). The recorded emission peaks of the materials showed that the luminescence of the samples was green, with the luminescence intensity increasing when Tb3+ was introduced. The developed materials can find applications in medicine as bioimplants with a possibility of noninvasive visualization of the bone restoration process.

Achieving Efficient Optical Thermometry in Terbium‐Doped Highly Transparent Ceramics

AbstractTemperature‐responsive dynamics of excited‐state population in terbium (Tb) ions may open the door for the advancement of high‐performance photothermal feedback windows. However, obtaining robust luminescence and superior transparency in Tb‐doped ceramics continues to pose a formidable challenge, leaving them far away from photonic application. Here, to fill this important gap, the demonstration of Tb doped transparent ceramics for luminescent thermometric windows is reported. Y2Zr2O7:Tb (YZO:Tb) ceramics are used as an illustrative example. After a sequence of thermal treatments, the defect centers F/F+ and defect clusters [] and [] in these YZO:Tb transparent ceramics are eliminated, resulting in a notable enhancement of their in‐line transmittance from 71% to 76%, making it close to the theoretical limit. Moreover, the corresponding photoluminescence increased significantly, reaching a factor of 296 times. Furthermore, a temperature feedback window is designed using the excitation intensity ratio (EIR) or single‐band luminescence intensity ratio (SBLIR) mode, which presents high sensitivity (1.04%) and high repeatability (98%). This work not only provides a paradigm in the application of the Tb doped transparent ceramics for temperature sensing windows, but also suggests a pathway to build efficient thermometers based on excited state population deployment in window systems.

Optimization and Applications of Instrumental and Preconcentration Neutron Activation Analysis Methods for Rapid Determination of Selected REE by Utilizing their Short‐Lived Activation Products**

AbstractDetermination of Rare Earth Elements (REEs) using spectroscopic methods is challenging. Conventional Instrumental Neutron Activation Analysis (INAA) method utilizing Pneumatic Carrier Facility (PCF) of Dhruva research reactor has been optimized with the short‐lived isotopes such as 161Gd, 165mDy and 153/155Sm for quantification of Gd, Dy and Sm respectively. Such isotopes are difficult to observe by conventional INAA with longer cooling periods owing to their very short half‐lives (1–3 mins). In this work, such isotopes are not only observed but also utilized as activation product for rapid determination of these REEs. The standardized method has been utilized for the first time in liquid samples involving nuclear fuel like U3O8 wherein TBP/n‐dodecane has been applied for chemical separation of Uranium prior to analysis. The INAA method has also been applied for validating the stoichiometry of Gd in Gd3+ co‐doped Zn2P2O7:Tb3+ green emitting solid‐state phosphors, which plays a very pivotal role in sensitizing the terbium ion in its performance for solid state lighting. We believe with huge current demand of REEs in research, science and technology; INAA can be a game changer wherever needed for quantification with high precision and accuracy and can also be extended to other REEs of interest.