Microbial green synthesis of luminescent terbium sulfide nanoparticles using E. Coli: a rare earth element detoxification mechanism.

BACKGROUND: Rare-earth sulfide nanoparticles (NPs) could harness the optical and magnetic features of rare-earth ions for applications in nanotechnology. However, reports of their synthesis are scarce and typically require high temperatures and long synthesis times. RESULTS: Here we present a biosynthesis of terbium sulfide (TbS) NPs using microorganisms, identifying conditions that allow Escherichia coli to extracellularly produce TbS NPs in aqueous media at 37 °C by controlling cellular sulfur metabolism to produce a high concentration of sulfide ions. Electron microscopy revealed ultrasmall spherical NPs with a mean diameter of 4.1 ± 1.3 nm. Electron diffraction indicated a high degree of crystallinity, while elemental mapping confirmed colocalization of terbium and sulfur. The NPs exhibit characteristic absorbance and luminescence of terbium, with downshifting quantum yield (QY) reaching 28.3% and an emission lifetime of ~ 2 ms. CONCLUSIONS: This high QY and long emission lifetime is unusual in a neat rare-earth compound; it is typically associated with rare-earth ions doped into another crystalline lattice to avoid non-radiative cross relaxation. This suggests a reduced role of nonradiative processes in these terbium-based NPs. This is, to our knowledge, the first report revealing the advantage of biosynthesis over chemical synthesis for Rare Earth Element (REE) based NPs, opening routes to new REE-based nanocrystals.

Terbium- and samarium-doped Li2ZrO3 perovskite materials as efficient and stable electrocatalysts for alkaline hydrogen evolution reactions.

The preparation of highly active, rare earth, non-platinum-based catalysts for hydrogen evolution reactions (HER) in alkaline solutions would be useful in realizing green hydrogen production technology. Perovskite oxides are generally regarded as low-active HER catalysts, owing to their unsuitable hydrogen adsorption and water dissociation. In this article, we report on the synthesis of Li2ZrO3 perovskites substituted with samarium and terbium cations at A-sites for the HER. LSmZrO3 (LSmZO) and LTbZrO3 (LTbZO) perovskite oxides are more affordable materials, starting materials in abundance, environmentally friendly due to reduced usage of precious metal and moreover have potential for several sustainable synthesis methods compared to commercial Pt/C. The surface and elemental composition of the prepared materials have been confirmed by X-ray photoelectron spectroscopy (XPS). The morphology and composition analyses of the LSmZO and LTbZO catalysts showed spherical and regular particles, respectively. The electrochemical measurements were used to study the catalytic performance of the prepared catalyst for hydrogen evolution reactions in an alkaline solution. LTbZO generated 2.52 mmol/g/h hydrogen, whereas LSmZO produced 3.34 mmol/g/h hydrogen using chronoamperometry. This was supported by the fact that the HER electrocatalysts exhibited a Tafel slope of less than 120 mV/dec in a 1.0 M alkaline solution. A current density of 10 mA/cm2 is achieved at a potential of less than 505 mV. The hydrogen production rate of LTbZO was only 58.55%, whereas LSmZO had a higher Faradaic efficiency of 97.65%. The EIS results demonstrated that HER was highly beneficial to both electrocatalysts due to the relatively small charge transfer resistance and higher capacitance values.

Eu/Tb-MOF as fluorescence sensors for the detection homocysteine in human serum performance and mechanistic investigation.

Abnormal homocysteine (Hcy) levels in human serum have been associated with serious or vital diseases, making the reliable and easy detection of Hcy important to clinical analysis and biological study. In this work, five phosphorescent Ir(C^N)2(N^N) complexes (Irn) having aldehyde group were synthesized as probes (C^N and N^N denoted ligands). A discussion was conducted on their molecular structure, electronic structure, photophysical parameters, and Hcy sensing ability, revealing the correlations between their molecular structures and performances. Irn emission was enhanced (by âˆ¼ two folds) and blue-shifted (by 100 nm) after meeting Hcy (free state), via a cyclization reaction between the -CHO group (from Irn) and Hcy. In addition, using RE(BTC) as a supporting material (RE = Tb and Eu), the Ir(III) probe was loaded onto a supporting material of RE(BTC) (H3BTC = 1, 3, 5-benzenetricarboxylic acid). The emission color was changed by increasing Hcy concentration. Straight working curves were obtained with LOD (limit of detection) of 1.9 µM and a response time of ∼200 s. The novelty of this work was the combination of Irn with RE(BTC), which offered enhanced and blue-shifted emission upon Hcy via a cyclization reaction. This demonstrated a high level of sensitivity towards homocysteine detection.

A ratiometric fluorescence sensor with different responsive modes based on carbon dots-embedded Tb-MOFs for the determination of norfloxacin and levofloxacin.

Norfloxacin (NOR) and levofloxacin (LEV) are the two most frequently used fluoroquinolones (FQs) in clinic. Their residues seriously endanger the ecosystem and human health. Due to their similarity in structure and properties, it is urgent to develop an efficient and sensitive strategy for detection and differentiation. Herein, we synthesized a novel ratiometric fluorescent sensor for the first time by combining N, S co-doped carbon dots (CDs) and the precursors of Tb-MOFs through a facile one-pot method. The introduction of CDs effectively facilitated the energy transfer between Tb3+ and FQs, overcoming the limitation that single Tb-MOFs could not identify similar antibiotics. Specifically, the presence of NOR resulted in reverse signal response through the inner filter effect and antenna effect. The synergistic effect of these two mechanisms contributed to achieving signal amplification accompanied by a distinguishable color transition. The limit of detection (LOD) was 0.036 µM. Different from NOR, the addition of LEV reduced the electron density of the system, weakened the coordination ability of Tb3+ with LEV, and induced a single signal response with Tb3+ fluorescence intensity as a reference signal (LOD = 0.383 µM). Furthermore, the method proved to be rapid and visual, allowing for the straightforward analysis of FQs residues in water, food matrices, and biological samples with satisfactory precision. By integrating N, S-CDs@Tb-MOFs with flexible substrates, the paper-based sensor facilitated the visual quantitative determination of FQs by reading RGB values. The developed sensor presents a promising strategy for the identification and real-time monitoring of antibiotics.

Fluorescence array sensor based on lanthanide complex for pattern recognition detection of fluoroquinolone antibiotics.

Fluoroquinolone antibiotics, a class of animal and human useful antibiotics, are widely utilized in numerous fields including biomedical science, animal husbandry, and aquatic finfish farming. Its high demand and wide application have directly or indirectly led to substantial consumption and discharge of antibiotics, affecting not only the environment but also endangering human health through bioaccumulation. Hence, rapid and precise detection of trace antibiotics in water, food, and biological samples is critically important. This research synthesized Tb3+/Eu3+ complexes with dual emission centers, and a fluorescence sensor array was constructed with the fluorescence intensity ratio F1/F2 of the two emission centers as a signal. Different sensitization effect of fluoroquinolone antibiotics towards lanthanide complexes aided in differentiating five fluoroquinolone antibiotics from two others. Additionally, the sensor array can effectively detect fluoroquinolone antibiotics in real samples, suggesting its reliability and practicality of complex sample analysis. The excellent qualitative and quantitative analysis ability of this strategy for fluoroquinolone antibiotics offers a novel perspective for antibiotic residue detection, showcasing a new opportunity for lanthanide complex application in sensor arrays.

Adsorption of terbium (III) on DGA and LN resins: Thermodynamics, isotherms, and kinetics.

Two commercially available extraction chromatography (EXC) resins containing N,N,N',N'-tetra-n-octyldiglycolamide (DGA Resin, Normal, 50 - 100 µm) and Bis(2-ethylhexyl) phosphate (LN Resin, 100 - 150 µm) were used as adsorbents to study fundamental adsorption properties such as thermodynamic values, equilibrium isotherms, and kinetic uptake models for terbium(III) adsorption. Weight distribution ratios (Dw) for terbium on DGA and LN resins were measured using a [160Tb]Tb3+radiometric tracer in nitric acid as a function of acidity, temperature, initial analyte concentration, and equilibrium time. The Dw values showed increasing binding affinity for DGA resin at high nitric acid concentrations and decreasing binding affinity for LN resins. Thermodynamic studies for DGA and LN resins revealed that the Gibbs free energy (ΔG) increased consistently with temperature. To model equilibrium data, increasingly higher parameter equilibrium isotherm models (Henry (1) < Langmuir, Freundlich (2) < Redlich-Peterson (3) < Fritz-Schluender (4)) were compared on their root mean squared errors (RMSE) and adjusted determination coefficients to determine the most applicable model. In all cases, the empirical four-parameter Fritz-Schluender isotherm demonstrated a superior fit. Similar comparisons for reaction-based kinetic models (Pseudo-first-order < Pseudo-second-order < Pseudo-n-order) revealed that the higher-order PNO model yielded a superior fit of kinetic data for both resins. However, in some cases, adsorption isotherms and kinetic models could also be modeled by a lower-order model with minimal change in error parameters. Weber-Morris plots revealed that two linear sections are observed for each resin, where the first linear segment is attributed to fast (film diffusion) adsorption of terbium, followed by slower intraparticle diffusion of terbium through the pores as the rate-limiting step. Based on the Weber-Morris plot, both film and intraparticle diffusion are involved in controlling the kinetic rate of adsorption for DGA and LN resins.

Skin-attachable Tb-MOF ratio fluorescent sensor for real-time detection of human sweat pH.

The pH of human sweat is highly related with a variety of diseases, whereas the monitoring of sweat pH still remains challenging for ordinary families. In this study, we developed a novel dual-emission Tb-MOF using DPA as the ligand and further designed and constructed a skin-attachable Tb-MOF ratio fluorescent sensor for real-time detection of human sweat pH. With the increased concentration of H+, the interaction of H+ with carbonyl organic ligand leads to the collapse of the Tb-MOF crystal structure, resulting in the interruption of antenna effect, and correspondingly increasing the emission of the ligand at 380 nm and decreasing the emission of the central ion Tb3+ at 544 nm. This Tb-MOF nanoprobe has a good linear response in the pH range of 4.12-7.05 (R2 = 0.9914) with excellent anti-interference ability. Based on the merits of fast pH response and high sensitivity, the nanoprobe was further used to prepare flexible wearable sensor. The wearable sensor can detect pH in the linear range of 3.50-6.70, which covers the pH range of normal human sweat (4.50-6.50). Subsequently, the storage stability and detection accuracy of the sensors were evaluated. Finally, the sensor has been successfully applied for the detection of pH in actual sweat samples from 21 volunteer and the real-time monitoring of pH variation during movement processing. This skin-attachable Tb-MOF sensor, with the advantages of low cost, visible color change and long shelf-life, is appealing for sweat pH monitoring especially for ordinary families.

Boric acid functionalized Fe3O4@CeO2/Tb-MOF as a luminescent nanozyme for fluorescence detection and degradation of caffeic acid.

Caffeic acid (CA) is a natural polyphenol that can have various positive effects on human health. However, its extraction and processing can cause significant ecological issues. Therefore, it is crucial to detect and degrade CA effectively in the environment. In this study, we have developed a multifunctional magnetic luminescent nanozyme, Fe3O4@CeO2/Tb-MOF, which combines peroxidase activity to detect and degrade CA. The fluorescence of the nanozyme was significantly attenuated due to the specific nucleophilic reaction between its boronic acid moiety and the o-diphenol hydroxyl group of CA, energy competition absorption and photo-induced electron transfer (PET) effect. This nanozyme demonstrates a linear detection range from 50 nM to 500 µM and an exceptionally low detection limit of 18.9 nM, along with remarkable selectivity and stability. Moreover, the synergistic catalysis of Fe3O4 and CeO2 within Fe3O4@CeO2/Tb-MOF fosters peroxidase activity, leading to the generation of substantial free radicals catalyzed by H2O2, which ensures the efficient degradation of CA (∼95%). The superparamagnetic property of Fe3O4 further enables the efficient reuse and recycling of the nanozyme. This research provides a novel approach for the concurrent detection and remediation of environmental contaminants.

Low-potential anodic electrochemiluminescence of terbium metal-organic frameworks for selective microRNA-155 detection.

High excitation potential is recognized as a harmful factor for the biological activity of biomacromolecules, such as proteins and nucleic acids, in electrochemiluminescence (ECL) biosensing. Developing low-potential ECL luminophores is vital for improving ECL accuracy in actual sample sensing. In this work, based on porous metal-organic framework (MOF) structure with multiple active sites and energy transfer between the excited ligands and Ln nodes, we designed a series of Ln-MOFs and observed ECL emission at low potential, providing a novel method to realize low-potential ECL. The MOF nanoemitters were prepared using 1,3,5-tri (4-carboxyphenyl)benzene ligand and several lanthanide ions as nodes through mild hydrothermal reaction. Interestingly, strong ECL emission at +0.75 V of peak potential was observed in the ECL-potential curve of Tb-based MOF using 2,2',2″-nitrilotriethanol as coreactant, which was beneficial for reducing background interference in biosensing, and this ECL emission was attributed to the energy transfer between Tb and excited ligand. This low-potential ECL was then applied to construct an ECL biosensor with newly developed Cas12a-based method for selective detection of microRNA-155 without the help of strand displacement or reverse transcription. For this ECL system, the limit of detection was 0.78 nM, and the overall detection time was 2.5 h. The Ln-MOF nanoemitter provides a robust ECL platform to selectively detect various targets by integrating new bio-related techniques.

Synthesis and Characterization of Folic Acid-Conjugated Terbium Complexes as Luminescent Probes for Targeting Folate Receptor-Expressing Cells.

Several conjugates between folic acid and a series of kinetically stable lanthanide complexes have been synthesized, using amide coupling and azide-alkyne cycloaddition methodologies to link the metal-binding domain to folate through a variety of spacer groups. While all these complexes exhibit affinity for the folate receptor, it is clear that the point of attachment to folate is essential, with linkage through the γ-carboxylic acid giving rise to significantly enhanced receptor affinity. All the conjugates studied show affinities consistent with displacing biological circulating folate derivatives, 5-methyltetrahydrofolate, from folate receptors. All the complexes exhibit luminescence with a short-lived component arising from ligand fluorescence overlaid on a much longer lived terbium-centered component. These can be separated using time-gating methods. From the results obtained, the most promising approach to achieve sensitized luminescence in these systems requires incorporating a sensitizing chromophore close to the lanthanide.

Luminescence "Turn-On" Sensing of Brain Natriuretic Peptide (BNP) - Dilated Cardiomyopathy Biomarker Based on the MoS2 Nanosheet Quenched Terbium Citrate Complex.

Dilated cardiomyopathy (DCM), known as myocardial metabolic dysfunction, is recognized as a clinical condition characterized by left ventricular dilation or improper contraction of cardiac muscles in the absence of coronary atherosclerosis and hypertension. It is an independent risk factor for cardiac function caused by a hyperglycemic condition in diabetic patients leading to heart failure (HF), which renders the early diagnosis of DCM highly challenging. Hence, detection of early diagnostic biomarkers in blood serum to identify DCM conditions is quite requisite. Brain natriuretic peptide (BNP) is a well-recognized biomarker for heart failure and reported as an early diagnostic biomarker for DCM. In this work, we developed a terbium citrate based MoS2 nanosheet (NS) coupled immunoprobe for the sensitive detection of BNP. The antibody conjugated Tb-citrate complex exhibits green fluorescence, which is quenched by the introduction of MoS2 NS. On subsequent addition of antigen BNP, the fluorescence is enhanced because of specific antigen-antibody interaction. The probe is selective and sensitive toward BNP in a linear range from 30.76 to 849.85 pg/mL with a low LOD of 3.87 pg/mL. The probe is validated in spiked human serum samples with good recovery percentage.

Comparative study of 155Tb production via 155Dy precursor with p, d and α beams on natural targets for medical applications.

Three different reactions with the use of natural targets are investigated to produce 155Tb for medical applications from the decay of its precursor 155Dy. The TALYS code has been exploited to optimize the cross section description and to improve the agreement with the full set of available data. The study is completed by a theoretical model for the two radio-chemical separations: optimal solutions are presented for the production of high quality 155Tb samples, guaranteed by the absence of the main contaminant, 156Tb.

Tb3+ assisted dithioerythritol stabilized copper nanocluster with AIE behavior for ratiometric fluorescent determination of fluoroquinolones.

BACKGROUND: Fluoroquinolones (FQs) are widely used in livestock and poultry industry because of their satisfactory effects in preventing and treating bacterial infection. However, due to irrational use and poor biodegradability, FQs can easily remain in food animals and further enter the human body through the food chain. Therefore, accurate and sensitive detection of FQs residues in animal-origin food is significant. The traditional methods commonly used for FQs detection have some limitations. Ratiometric fluorescence detection technology has the advantages of fast, sensitive, self-correcting, and easy visualization. However, the reports on the use of ratiometric fluorescence probes for FQs detection are limited. RESULTS: In this work, a novel probe was proposed for ratiometric fluorescent analysis of FQs. In this probe, the fluorescence of dithioerythritol stabilized copper nanoclusters (DTE-Cu NCs) was significantly enhanced due to the Tb3+ triggered aggregation-induced emission effect. FQs bound Tb3+ in Tb3+/DTE-Cu NCs through carboxyl and carbonyl groups, so that Tb3+ was effectively sensitized to emit green fluorescence. However, the red fluorescence of DTE-Cu NCs was not interfered. The fluorescence of the probe transformed from red to green with the increase of FQs concentration. Using norfloxacin (NOR), difloxacin (DIF), and enrofloxacin (ENR) as FQs simulants, this probe showed a sensitive linear response ranged from 0.025 to 22.5 µM, with the limits of detection of 9.6 nM, 9.3 nM, and 7.7 nM. The application potential for FQs detection was verified via a standard addition assay of egg samples with the recovery rate of 90.4 %-114.7 %. SIGNIFICANT: The fluorescence probe based on Tb3+/DTE-Cu NCs is expected to realize the ratiometric fluorescence sensitive detection of FQs. The establishment of this simple, effective, and rapid detection platform opens up a new way for the detection of FQs residues in animal-origin foods, and also provides a new idea for the design of rapid detection platforms for other hazard factors.

Fabrication of a Terbium-Functionalized Cadmium Organic Framework with Proper Energy Levels as a Ratiometric Probe of an Anthrax Biomarker.

Anthrax bacillus is a very dangerous zoonotic pathogen that seriously endangers public health. Rapid and accurate qualitative and quantitative detection of its biomarkers, 2,6-dipicolinic acid (DPA), is crucial for the prevention and treatment of this pathogenic bacterium. In this work, a novel Cd-based MOF (TTCA-Cd) has been synthesized from a polycarboxylate ligand, [1,1':2',1″-terphenyl]-4,4',4″,5'-tetracarboxylic acid (H4TTCA), and further doped with Tb(III), forming a dual-emission lanthanide-functionalized MOF hybrid (TTCA-Cd@Tb). TTCA-Cd@Tb can be developed as a high-performance ratiometric fluorescent sensor toward DPA with a very low detection limit of 7.14 nM and high selectivity in a wide detection range of 0-200 µM, demonstrating a big advancement and providing a new option for the detection of DPA.

Magnetic lanthanide sensor with self-ratiometric time-resolved luminescence for accurate detection of epithelial cancerous exosomes.

Fluorescence-based LB (liquid biopsy) offers a rapid means of detecting cancer non-invasively. However, the widespread issue of sample loss during purification steps will diminish the accuracy of detection results. Therefore, in this study, we introduce a magnetic lanthanide sensor (MLS) designed for sensitive detection of the characteristic protein, epithelial cell adhesion molecule (EpCAM), on epithelial tumor exosomes. By leveraging the inherent multi-peak emission and time-resolved properties of the sole-component lanthanide element, combined with the self-ratiometric strategy, MLS can overcome limitations imposed by manual operation and/or sample complexity, thereby providing more stable and reliable output results. Specifically, terbium-doped NaYF4 nanoparticles (NaYF4:Tb) and deformable aptamers terminated with BHQ1 were sequentially introduced onto superparamagnetic silica-decorated Fe3O4 nanoparticles. Prior to target binding, emission from NaYF4:Tb at 543 nm was partially quenched due to the fluorescence resonance energy transfer (FRET) from NaYF4:Tb to BHQ1. Upon target binding, changes in the secondary structure of aptamers led to the fluorescence intensity increasing since the deconfinement of distance-dependent FRET effect. The characteristic emission of NaYF4:Tb at 543 nm was then utilized as the detection signal (I1), while the less changed emission at 583 nm served as the reference signal (I2), further reporting the self-ratiometric values of I1 and I2 (I1/I2) to illustrate the epithelial cancerous features of exosomes while ignoring possible sample loss. Consequently, over a wide range of exosome concentrations (2.28 × 102-2.28 × 108 particles per mL), the I1/I2 ratio exhibited a linear increase with exosome concentration [Y(I1/I2) = 0.166 lg (Nexosomes) + 3.0269, R2 = 0.9915], achieving a theoretical detection limit as low as 24 particles per mL. Additionally, MLS effectively distinguished epithelial cancer samples from healthy samples, showcasing significant potential for clinical diagnosis.

Concentration-dependent luminescence characterization of terbium-doped strontium aluminate nanophosphors.

The present investigation describes the synthesis of luminescent terbium-doped strontium aluminate nanoparticles emitting bright green light, which were synthesized through a solid-state reaction method assisted by microwave radiation. Various samples containing different concentrations of Tb were synthesized, and an analysis of their structural and morphological features was conducted using powder x-ray diffraction, Fourier transform infrared spectroscopy and field emission scanning electron microscopy. The band gaps of the samples were determined utilizing the Kubelka-Munk method. The quenching mechanism observed was identified to be due to dipole-dipole interaction using the Dexter theory. The optimized sample with a terbium concentration of 4 at.% has a luminescence lifetime of 1.05 ms with 20.62% quantum efficiency. The results of this study indicate that the terbium-doped strontium aluminate fluorescent nanoparticles exhibit promising potential for a wide range of applications, including bioimaging, sensing and solid-state lighting.

A green approach to encapsulate proteins and enzymes within crystalline lanthanide-based Tb and Gd MOFs.

In this work, bovine serum albumin (BSA) and Aspergillus sp. laccase (LC) were encapsulated in situ within two lanthanide-based MOFs (TbBTC and GdBTC) through a green one-pot synthesis (almost neutral aqueous solution, T = 25 °C, and atmospheric pressure) in about 1 h. Pristine MOFs and protein-encapsulated MOFs were characterized through wide angle X-ray scattering, scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared and Raman spectroscopies. The location of immobilized BSA molecules, used as a model protein, was investigated through small angle X-ray scattering. BSA occurs both on the inner and on the outer surface of the MOFs. LC@TbBTC, and LC@GdBTC samples were also characterized in terms of specific activity, kinetic parameters, and storage stability both in water and acetate buffer. The specific activity of LC@TbBTC was almost twice that of LC@GdBTC (10.8 µmol min-1 mg-1vs. 6.6 µmol min-1 mg-1). Both biocatalysts showed similar storage stabilities retaining ∼60% of their initial activity after 7 days and ∼20% after 21 days. LC@TbBTC dispersed in acetate buffer exhibited a higher storage stability than LC@GdBTC. Additionally, terbium-based MOFs showed interesting luminescent properties. Together, these findings suggest that TbBTC and GdBTC are promising supports for the in situ immobilization of proteins and enzymes.

Enrichment of Terbium(III) under synergistic effect of biosorption and biomineralization by Bacillus sp. DW015 and Sporosarcina pasteurii.

Biosorption and biomineralization are commonly used for the immobilization of metal ions. Biosorption is commonly used as a green method to enrich rare earth ions from wastewater. However, little attention has been paid to the facilitating role of biomineralization in the enrichment of rare earth ions. In this study, a strain of Bacillus sp. DW015, isolated from ion adsorption type rare earth ores and a urease-producing strain Sporosarcina pasteurii were used to enrich rare earth elements (REEs) from an aqueous solution. The results indicate that biomineralization accelerates the enrichment of Terbium(III) compared to biosorption alone. Kinetic analysis suggests that the main mode of action of DW015 was biosorption, following pseudo-second-order kinetics (R2 = 0.998). The biomineralization of DW015 did not significantly contribute to the enrichment of Tb(III), whereas excessive biomineralization of S. pasteurii led to a decrease in the enrichment of Tb(III). A synergistic system of biosorption and biomineralization was established by combining the two bacteria, with the optimal mixed bacteria (S. pasteurii:DW015) ratio being 1:19. This study provides fundamental support for the synergistic effect of biosorption and biomineralization and offers a new reference for future microbial-based enrichment methods. IMPORTANCE: A weak microbially induced calcium carbonate precipitation (MICP) promotes the enrichment of Tb(III) by bacteria, while a strong MICP leads to the release of Tb(III). However, existing explanations cannot elucidate these mechanisms. In this study, the morphology of the bioprecipitation and the degree of Tb(III) enrichment were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). The data revealed that MICP could drive stable attachment of Tb(III) onto the cell surface, forming a Tb-CaCO3 mixed solid phase. Excessive rapid rate of calcite generation could disrupt the Tb(III) adsorption equilibrium, leading to the release of Tb(III). Therefore, in order for Tb(III) to be stably embedded in calcite, it is necessary to have a sufficient number of adsorption sites on the bacteria and to regulate the rate of MICP. This study provides theoretical support for the process design of MICP for the enrichment of rare earth ions.

Oxolinic Acid Generated Green Fluorescence Based on a Terbium-Functionalized Covalent Organic Framework.

Oxolinic acid (OXO), a classic environmental contaminant, has a terrible detrimental effect on human health. The exploration of efficient strategies to detect and detecting OXO has remarkable significance. Herein, we reported a novel terbium(III)-functionalized covalent organic framework (Bpy-DhBt-COF@Tb3+) by fixing Tb3+ on the bipyridine-connecting COF (Bpy-DhBt-COF) as a turn-on fluorescent switch toward OXO for the first time. In this platform, Tb3+ acts as the specific recognition units for OXO and the response signal, while Bpy-DhBt-COF acts as the safehaven for Tb3+. Once introducing OXO to Bpy-DhBt-COF@Tb3+, OXO can instead water molecules coordinate with Tb3+ and sensitize Tb3+ instantly, thereby producing a significant fluorescence signal. Profiting from the excellent porosity of Bpy-DhBt-COF@Tb3+, it can obtain optimal response toward OXO only within 10 s with an ultrasensitive detection limit of 12.5 nM. Furthermore, Bpy-DhBt-COF@Tb3+ displayed outstanding selectivity toward OXO than other general quinolones. Based on these, a Tb3+-based COF was explored for the first time for the turn-on fluorescence detection of an OXO with rapid response, high sensitivity, and outstanding selectivity. In this work, we not only exhibit the attractive performance of Tb3+-functionalized COF to detect OXO but also propose a prospect strategy for creating other fluorescent sensors for multiple targets.

Dual-mode biosensor using Tb-Cu MOF@Au nanoenzyme to effectively quench the photocurrent of Bi2O3/Bi2S3/AgBiS2 heterojunction and emit fluorescence for neuron-specific enolases detection.

A novel dual-mode biosensor was constructed for the ultrasensitive detection of neuron-specific enolase (NSE), utilizing Tb-Cu MOF@Au nanozyme as the signal label to effectively quench the photoelectrochemical (PEC) signals of Bi2O3/Bi2S3/AgBiS2 composites and initiate fluorescent (FL) signals. First, Bi2O3/Bi2S3/AgBiS2 heterojunction with excellent photoelectric activity was selected as the substrate material to provide a stable photocurrent. The well-matched energy levels significantly enhanced the separation and transfer of photogenerated carriers. Second, a strategy of consuming ascorbic acid (AA) by Tb-Cu MOF@Au nanozyme was introduced to improve the sensitivity of the PEC/FL biosensor. Tb-Cu MOF@Au not only could catalyze the oxidation of AA, but the steric effect further reduced the contact of AA with the substrate. More importantly, in the presence of H2O2, a significant fluorescence was produced from Tb3+ sensitized by the oxidation products of AA. Based on the above strategies, a highly stable and sensitive dual-mode biosensor was proposed for accurate NSE determination. Third, the developed dual-mode biosensor demonstrated excellent performance in detecting NSE. In this study, the PEC method demonstrated a wide detection range from 0.00005 to 200 ng/mL with a low detection limit of 20 fg/mL. The FL method exhibited a linear range from 0.001 to 200 ng/mL with a detection limit of 0.65 pg/mL. The designed biosensor showed potential practical implications in the accurate detection of disease markers.