Insight into effects of terbium on cell growth, sporulation and spore properties of Bacillus subtilis.

Recovery of rare earth elements (REEs) from wastewater with Bacillus subtilis (B. subtilis) during culture is promising due to its environmental benefits. However, the effects of REEs in the culture media on B. subtilis are poorly understood. This study aims to investigate the effects of the terbium (Tb(III)), a typical rare earth element, on the cell growth, sporulation, and spore properties of B. subtilis. Tb(III) can suppress bacterial growth while enhancing spore tolerance to wet heat. Spore germination and content of dipicolinic acid (DPA) were promoted at low concentrations of Tb(III) while inhibited at a high level, but an inverse effect on initial sporulation appeared. Scanning electron microscope and energy dispersive spectrometer detection indicated that Tb(III) complexed cells or spores and certain media components simultaneously. The germination results of the spores after elution revealed that Tb(III) attached to the spore surface was a key effector of spore germination. In conclusion, Tb(III) directly or indirectly regulated both the nutrient status of the media and certain metabolic events, which in turn affected most of the properties of B. subtilis. Compared to the coat-deficient strain, the wild-type strain grew faster and was more tolerant to Tb(III), DPA, and wet heat, which in turn implied that it was more suitable for the recovery of REEs during cultivation. These findings provide fundamental insights for the recovery of rare earths during the culture process using microorganisms.

Comparison of Photophysical Properties of Lanthanide(III) Complexes of DTTA- or DO3A-Appended Aryl-2,2'-Bipyridines.

New Tb(III) and Eu(III) complexes based on aryl-2,2'-bipyridine ligands with a cyclic DO3A chelating unit appended in the alpha position of the bipyridine core were synthesized. The photophysical properties of these complexes were compared with those of complexes of ligands with identical aryl-2,2'-bipyridine chromophores, but with an acyclic DTTA residue as an additional chelating site in the alpha position of the bipyridine core. The nature of the polyaminocarboxylic acid fragments was found to have a significant influence on the luminescence. For some of the Eu(III) complexes, upon the transition from acyclic DTTA- to the cyclic DO3A-appended ligands, a noticeable increase in the intensity of Eu(III) luminescence was observed, with an increase in the quantum yield of up to 2.55 times. In contrast, for most of the Tb(III) complexes, a similar transition resulted in a noticeable decrease in the luminescence intensity of the Tb(III) cation.

Luminescent Coordination Polymer for Picric Acid Detection and Treatment on Spinal Cord Injury Model Via Upregulating the trka Expression.

A luminescent coordination polymer based on Tb(III) has been synthesized with the tripodal carboxylic acid ligand containing N,O codonors (H2PBA = 5-[4-pyridin-3-yl-benzoylamino]-isophthalic acid) as ligand under solvothermal conditions. The chemical formula of this polymer is {[Tb2(PBA)3(H2O)3]·DMF·3H2O}n (1). Complex 1 has good sensitivity and selectivity to picric acid (PA). At 0-30 µmol/L, 1's quenching constant is 4.5 × 104 L/mol. In the biological function study, the motor function of spinal cord-injured animals after different treatments was evaluated using the blood-brain barrier (BBB) method. The trka expression level on the neural stem cells after treatment was measured to reveal the underlying mechanism.

Exploring the interactions of a Tb(III)-quercetin complex with serum albumins (HSA and BSA): spectroscopic and molecular docking studies.

Serum albumins (human serum albumin (HSA) and bovine serum albumin (BSA), two main circulatory proteins), are globular and monomeric macromolecules in plasma that transport many drugs and compounds. In the present study, we investigated the interactions of the Tb(III)-quercetin (Tb-QUE) complex with HSA and BSA using common spectroscopic techniques and a molecular docking study. Fluorescence data revealed that the inherent fluorescence emission of HSA and BSA was markedly quenched by the Tb-QUE complex through a static quenching mechanism, confirming stable complex formation (a ground-state association) between albumins and Tb-QUE. Binding and thermodynamic parameters were obtained from the fluorescence spectra and the related equations at different temperatures under biological conditions. The binding constants (Kb ) were calculated to be 0.8547 × 103 M-1 for HSA and 0.1363 × 103 M-1 for BSA at 298 K. Also, the number of binding sites (n) of the HSA/BSA-Tb-QUE systems was obtained to be approximately 1. Thermodynamic data calculations along with molecular docking results indicated that electrostatic interactions have a main role in the binding process of the Tb-QUE complex with HSA/BSA. Furthermore, molecular docking outputs revealed that the Tb-QUE complex has high affinity to bind to subdomain IIA of HSA and BSA. Binding distances (r) between HSA-Tb-QUE and BSA-Tb-QUE systems were also calculated using the Forster (fluorescence resonance energy transfer) method. It is expected that this study will provide a pathway for designing new compounds with multiple beneficial effects on human health from the phenolic compounds family such as the Tb-QUE complex.

Luminescent nanoparticles for rapid monitoring of endogenous acetylcholine release in mice atria.

The present work introduces for the first time a nanoparticulate approach for ex vivo monitoring of acetylcholinesterase-catalyzed hydrolysis of endogenous acetylcholine released from nerve varicosities in mice atria. Amino-modified 20-nm size silica nanoparticles (SNs) doped by luminescent Tb(III) complexes were applied as the nanosensors. Their sensing capacity results from the decreased intensity of Tb(III)-centred luminescence due to the quenching effect of acetic acid derived from acetylcholinesterase-catalyzed hydrolysis of acetylcholine. Sensitivity of the SNs in monitoring acetylcholine hydrolysis was confirmed by in vitro experiments. Isolated atria were exposed to the nanosensors for 10 min to stain cell membranes. Acetylcholine hydrolysis was monitored optically in the atria samples by measuring quenching of Tb(III)-centred luminescence by acetic acid derived from endogenous acetylcholine due to its acetylcholinesterase-catalyzed hydrolysis. The reliability of the sensing was demonstrated by the quenching effect of exogenous acetylcholine added to the bath solution. Additionally, no luminescence quenching occurred when the atria were pre-treated with the acetylcholinesterase inhibitor paraoxon.

Photoluminescence profiles and fast/slow annealing effects of Eu(III)/Tb(III)-codoped silica phosphor materials.

A silica (SiO2) nanoparticle matrix was codoped with luminescent Eu(III) and Tb(III) ions using a modified Stöber method. The effects of fast and slow thermal annealing on photoluminescence profile imaging were examined. Slow annealing treatment suppressed more quenching sites than fast thermal annealing to further increase the photoluminescence signals. The photoluminescence signals observed between 450 and 720 nm were assigned to the (5)D(0) → (7)F(J) (J = 0,1,2,3,4) of Eu(III) and the (5)D(4) → (7)F(J) (J = 6,5,4,3) transitions of Tb(III). Photoluminescence was largely sensitized by indirect excitation and was much stronger than that generated by direct excitation. The Eu(III) and Tb(III) ions were doped at lower symmetry sites in the silica matrix.

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.

Effect of structure on sensing performance of nitro explosives with high sensitivity and mechanism of two Tb(III) coordination polymers.

The use of a conjugate N-containing ligand resulted in the decreasing of structural dimensions from 2D network of [Tb(2-pyia)(Ac)(H2O)] (CP1) to 1D chain [Tb(2-pyia)(Ac)(IDP)] (CP2) (2-H2pyia = 5-(pyridin-2-ylmethoxy) isophthalic acid and IDP=imidazo[4,5-f]-[1,10] phenanthroline). Both of them exhibit the characteristic luminescence of Tb ions and could have high fluorescence sensing properties for cefixime and fluridine. The different sensing properties for nitro explosives are manifested as CP1 for nitrobenzene and CP2 for 4-nitrophenol due to the difference in structure. Furthermore, CP2 exhibits the ratiometric fluorescence sensing for Fe3+ ion with a low detection limit of 0.405 µM. The fluorescence sensing mechanism of the two Tb complexes for different analytes was investigated using experimental methods and theoretical calculations. CP1 was used for the detection of Flu residues in the actual system and better results were obtained. The work shows the introduction of the chelated ligand might affect the structural and sensing performance changes of coordination polymers.

Ratiometric emission of Tb(III)-functionalized Cd-based layered MOFs for portable visual detection of trace amounts of diquat in apples, potatoes and corn.

Diquat (DQ) is a typical bipyridine herbicide widely used to control weeds in fields and orchards. The severe toxicity of diquat poses a serious threat to the environment and human health. Metal-organic frameworks (MOFs) have received widespread attention due to their unique physical and chemical properties and applications in the detection of toxic and harmful substances. In this work, a two-dimensional (2D) Tb(III) functionalized MOF Tb(III)@1 (1 = [Cd(HTATB)(bimb)]n·H2O (Cd-MOF), H3TATB = 4,4',4″-triazine-2,4,6-tribenzoicacid, bimb = 1,4-bis((1H-imidazol-1-yl)methyl)benzene) has been prepared and characterized. Tb(III)@1 has excellent optical properties and high water and chemical stability. After the Tb(III) is fixed by the uncoordinated -COO- in the 1 framework, Tb(III)@1 emits the typical green fluorescence of the lanthanide ion Tb(III) through the "antenna effect". It is worth noting that Tb(III)@1 can be used as a dual emission fluorescence chemical sensor for the ratio fluorescence detection of pesticide DQ, exhibiting a relatively low detection limit of 0.06 nM and a wide detection range of 0-50 nM. After the addition of DQ, a rapid color change of Tb(III)@1 fluorescence from green to blue was observed due to the combined effects of IFE, FRET and dynamic quenching. Therefore, a simple test paper box has been designed for direct on-site determination of pesticide DQ. In addition, the developed sensor has been successfully applied to the detection of DQ in real samples (fruits a Yin-Xia Sun and Bo-Tao Ji contributed equally to this work and should be considered co-first authors.nd vegetables) with satisfactory results. The results indicate that the probe developed in this study has broad application prospects in both real sample detection and actual on-site testing.

Enhanced Tb(III) fluorescence on gelatin-coated silver nanoparticles in dopamine detection.

A composite fluorescent nanoprobe based on metal enhanced fluorescence (MEF) effect of gelatin-coated silver nanoparticles (AgNPs@gel) was developed for selective and sensitive detection of dopamine (DA). The characteristic fluorescence of Tb(III) was using as the detection signal and AgNPs@gel served as substrates of the MEF. Gelatin with rich amine and carboxylic groups was used not only as a co-ligand of Tb(III) complex, but also as a bridging substance and a spacing material for improving the MEF of AgNPs@gel on the intrinsic luminescent intensity of Tb(III). Under the optimal conditions, the increment of the fluorescence intensity (measured at 307/544 nm as excitation/emission wavelength) of the system increased linearly with the concentration of DA in the range of 0.80-100 nM (R2 = 0.9937) and 100-1000 nM (R2 = 0.9978). The fluorescent probe greatly improved Tb(III) luminescence, which paved the way for sensitive detection with a low detection limit of 0.54 nM. It also showed good selectivity among other neurotransmitters. This work was successfully applied to the determination of DA in human serum samples with recoveries ranging from 99.8 to 102.2%. We believe that the Tb(III)-DA-AgNPs@gel composite fluorescent probe can be developed as a new approach for DA detection.

Energy transfer mechanism in luminescence Eu(III) and Tb(III) complexes of coumarin-3-carboxylic acid: A theoretical study.

Excited state energy level diagrams of coumarin-3-carboxylic acid (HCCA) chromophore, Eu(CCA)Cl2(H2O)2 (1), Eu(CCA)2Cl(H2O)2 (2), Eu(CCA)3(H2O)3 (3), Tb(CCA)2Cl(H2O) (4) and Tb(CCA)2(NO3)(H2O) (5) in gas phase and polar solution have been calculated by means of DFT/TDDFT/ωB97XD methods. Based on these results, the ability of CCA to sensitize Eu(III) and Tb(III) luminescence has been examined. The competitive excited state processes in the complexes - fluorescence, intersystem crossing (ISC) and phosphorescence, were analyzed depending on the environment, number of the ligands, Ln(III) ion type (Eu and Tb) and counteranion (Cl- and NO3-). It has been found that the environment altered the S1 state energy, oscillator strength, fluorescence lifetime as well as the S1 character - polar solution stabilized the S1(ππ*) state, whereas non-polar solution (gas phase, solid state) stabilized the S1(nπ*) state. The S1(nπ*) state was decisive for the efficient energy transfer as it suppressed the S1 emission of CCA and favored ISC or direct transfer to the emitting levels of Eu(III). The HCCA triplet (T1) state minimum energy (~2.7, ~2.6ZPE eV) and (ππ*) character were retained in Eu/Tb-CCA complexes regardless of the environment. The energy gap between the higher energy T1 donor state and the acceptor levels 5D1 of Eu(III) (~0.5 eV) and 5D4 of Tb(III) (~0.1 eV) provided optimal resonance conditions for effective energy transfer for Eu(III), but less probability for Tb(III). The nonradiative energy (CCA â†’ Eu(III)) transfer rates and quantum luminescence yield for 2 and 3 were calculated by a strategy combining DFT geometries, INDO/S excitation energies and calculated Judd-Ofelt parameters. The excitation channel T1 â†’ 5D0 through an exchange mechanism was predicted as the most probable one to populate the main emissive Eu-centered state in complexes 2 and 3. The more efficient luminescence of 3 than that of 2 was discussed and explained.

Hydroxyapatite/NiFe2O4 superparamagnetic composite: Facile synthesis and adsorption of rare elements.

A magnetic hydroxyapatite composite (CaHAP/NF) derived from calcium hydroxyapatite [Ca10(PO4)6(OH)2] and nickel ferrite [NiFe2O4] was successfully synthesized by a coprecipitation method. The synthesized composite was characterized using Fourier transform infrared spectroscopy (FT-IR), X-Ray diffractometer (XRD), thermogravimetric differential thermal analysis (TG-DTA), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). Results clarify that the composite is a crystalline in nature, thermally stable up to 800 °C and possesses a high porous structure. The synthesized CaHAP/NF composite is a superparamagnetic material easily separated from aqueous solutions and would dissociate to some extent in strongly acidic conditions. The synthesized material was successfully applied as a solid phase for separation of Eu(III) and Tb(III) ions from aqueous solutions. The effect of various parameters (e.g. solution pH, equilibrium time and ionic strength) on sorption process was studied in static conditions. The synthesized sorbent could be considered as an efficient candidate for separation and recovery of Eu(III) and Tb(III). The sorption process was very fast initially, reached equilibrium within 6 h of contact and independent of ionic strength. The maximum sorption capacity values were 137.35 and 130.43 mg g-1 for Eu(III) and Tb(III), respectively. Desorption of Eu(III) and Tb(III) from loaded sample was studied using various eluents and maximum recovery was obtained using FeCl3 and EDTA solutions. More importantly, both FeCl3 and EDTA were individually applied as eluents in chromatographic separation of Eu(III) and Tb(III) in CaHAP/NF packed column and the best separation results were obtained by EDTA.

Tb(III) line intensities in multibubble sonoluminescence.

We observed the line emissions of trivalent terbium [Tb(III)] ions during multibubble sonoluminescence (MBSL) in the aqueous solutions of terbium chloride (TbCl3) under argon gas atmosphere. The line intensities of excited Tb(III) ions increased with TbCl3 concentration(mass percentage) in aqueous solutions. This phenomenon was interpreted qualitatively by numerically computing the Tb(III) line intensities in one sonoluminescing bubble among the cavitation bubbles in a liquid. The driving pressure for this sonoluminescing bubble was obtained by numerically solving the cavitation dynamic equation and bubble-pulsation equation. The Tb(III) ion line intensities obtained from the sonoluminescing bubble were attained by solving computing fluid dynamics equations and the spectral radiation formula.

Polyelectrolyte-coated ultra-small nanoparticles with Tb(III)-centered luminescence as cell labels with unusual charge effect on their cell internalization.

The present work reports ultra-small polyelectrolyte-coated water insoluble Tb(III) complex species with bright Tb(III)-centered luminescence resulted from efficient ligand-to-metal energy transfer as efficient labels for Hep-2 cells. The flow cytometry data revealed the enhanced cellular uptake of negatively charged nanoparticles coated by the polystyrenesulfonate (PSS)-monolayer versus the positively charged nanoparticles. The latter are obtained by layer-by-layer deposition of polyethyleneimine (PEI) onto PSS-coated ones. Confocal and TEM images of Hep-2 cells exposed by the colloids confirm favorable cell internalization of the PSS- compared to PEI-PSS-coated colloids illustrating unusual charge-effect. Dynamic light scattering data indicate significant effect of the biological background exemplified by serum bovine albumin and phosphatidylcholine-based bilayers on the exterior charge and aggregation behavior of the colloids. The obtained results reveal the PSS-coated nanoparticles based on water insoluble Tb(III) complex as promising cell labels.

A Novel Tb@Sr-MOF as Self-Calibrating Luminescent Sensor for Nutritional Antioxidant.

Sesamol, is well-known antioxidant and can reduce the rate of oxidation and prolong expiration date. It is also potentially antimutagenic and antihepatotoxic, the detection of sesamol is important and remains a huge challenge. Herein, a new 3D alkaline earth Sr metal organic framework [Sr(BDC)DMACH2O]n (BDC = benzene-1,4-dicarboxylate; DMAC = N,N-dimethylacetamide) is synthesized and a probe based on Tb3+ functionalized Sr-MOF. The Tb(3+)@Sr-MOF showed good luminescence and thermal property. Due to the energy competition between sesamol and ligand, the luminescence intensity of sesamol increases meantime luminescence intensity of Tb3+ decreases, the ratio of the emission intensities (I344/I545) linearly increases with sesamol in concentrations ranging from 1 × 10-7 to 8 × 10-4 M. Furthermore, the fluorescence-detected circular test shows that the composite Tb(3+)@Sr-MOF can serve as ratiometric sensor for sensing of sesamol. This is the first example for self-calibrated detecting sesamol based on metal-organic framework (MOF).

Targeted Nanoparticles for Selective Marking of Neuromuscular Junctions and ex Vivo Monitoring of Endogenous Acetylcholine Hydrolysis.

The present work for the first time introduces nanosensors for luminescent monitoring of acetylcholinesterase (AChE)-catalyzed hydrolysis of endogenous acetylcholine (ACh) released in neuromuscular junctions of isolated muscles. The sensing function results from the quenching of Tb(III)-centered luminescence due to proton-induced degradation of luminescent Tb(III) complexes doped into silica nanoparticles (SNs, 23 nm), when acetic acid is produced from the enzymatic hydrolysis of ACh. The targeting of the silica nanoparticles by α-bungarotoxin was used for selective staining of the synaptic space in the isolated muscles by the nanosensors. The targeting procedure was optimized for the high sensing sensitivity. The measuring of the Tb(III)-centered luminescence intensity of the targeted SNs by fluorescent microscopy enables us to sense a release of endogenous ACh in neuromuscular junctions of the isolated muscles under their stimulation by a high-frequency train (20 Hz, for 3 min). The ability of the targeted SNs to sense an inhibiting effect of paraoxon on enzymatic activity of AChE in ex vivo conditions provides a way of mimicking external stimuli effects on enzymatic processes in the isolated muscles.

Design and synthesis of a novel lanthanide fluorescent probe (TbIII-dtpa-bis(2,6-diaminopurine)) and its application to the detection of uric acid in urine sample.

In this study, a novel fluorescent probe, TbIII-dtpa-bis(2,6-diaminopurine) (Tb-dtpa-bdap), is designed based on the principle of complementary base pairing and synthesized for uric acid detection. The synthesized fluorescent probe is characterized by 1H NMR, 13C NMR, infra-red (IR) spectrum and ultraviolet-visible (UV-vis) spectra. It is found that the fluorescence of Tb-dtpa-bdap solution can be quenched obviously in the presence of uric acid. The affecting factors, including solution acidity, uric acid concentration and interfering substances, on the detection of uric acid using this probe are examined. Under optimized conditions, the fluorescence intensities of Tb-dtpa-bdap solution towards different uric acid concentrations show a linear response in the range from 1.00 × 10-5 mol·L-1 to 5.00 × 10-5 mol·L-1 with a linear correlation coefficient (R2) of 0.9877. And the obtained limit of detection (LOD) is about 5.80 × 10-6 mol·L-1, which is lower than the level of uric acid in actual urine. The mechanism on the detection of uric acid by using Tb-dtpa-bdap is inferred from the experimental results. The facts demonstrate that the proposed fluorescent probe can be successfully applied for the determination of uric acid in human urine samples.

Silver nanoprisms-based Tb(III) fluorescence sensor for highly selective detection of dopamine.

Dopamine (DA) is one of catecholamines and related to several neurological diseases. The selective determination for DA against other catecholamines is crucial in clinical diagnoses. In this work, a simple and reliable Tb(III)-based fluorescence sensor was constructed for the highly selective and sensitive detection of DA. Silver nanoprisms (AgNPrs) with suitable localized surface plasmon resonance bands were controllably synthesized to act as optimal platforms for surface enhanced fluorescence (SEF), while acetate was adopted to be a distance adjusting spacer for SEF and a recognizing component for DA. A fluorescence-enhanced Tb(III) composite sensor via the synergistic action of AgNPrs and acetate was finally obtained. The fluorescence signal was in proportion to the dopamine concentration in the range of 0.6-100nM (R2=0.9987) with a detection limit (S/N =3) of 0.22nM. Furthermore, the method exhibited good selectivity to DA among some amino acids, ions, other neurotransmitters, etc.

Luminescent silica nanoparticles for sensing acetylcholinesterase-catalyzed hydrolysis of acetylcholine.

This work highlights the H-function of Tb(III)-doped silica nanoparticles in aqueous solutions of acetic acid as a route to sense acetylcholinesterase-catalyzed hydrolysis of acetylcholine (ACh). The H-function results from H(+)-induced quenching of Tb(III)-centered luminescence due to protonation of Tb(III) complexes located close to silica/water interface. The H-function can be turned on/switched off by the concentration of complexes within core or nanoparticle shell zones, by the silica surface decoration and adsorption of both organic and inorganic cations on silica surface. Results indicate the optimal synthetic procedure for making nanoparticles capable of sensing acetic acid produced by enzymatic hydrolysis of acetylcholine. The H-function of nanoparticles was determined at various concentrations of ACh and AChE. The measurements show experimental conditions for fitting the H-function to Michaelis-Menten kinetics. Results confirm that reliable fluorescent monitoring AChE-catalyzed hydrolysis of ACh is possible through the H-function properties of Tb(III)-doped silica nanoparticles.

Interaction of metallacrown complexes with G-quadruplex DNA.

Interactions of the G-quadruplex (GQ) DNA with two pentacoordinate lanthanide (III) metallacrown (MC) complexes containing phenylalanine hydroxamic acid (pheHA) and copper(II) ions of the formula Eu 15-[MCCu,pheHA]-5 (1) and Tb 15-[MCCu,pheHA]-5 (2) were investigated. Binding of both metallacrowns to human telomeric G-quadruplex DNA was followed using CD spectroscopy, DNA melting profiles, and fluorescent intercalator displacement (FID) assay. A new G-quadruplex binding assay based of quenching of Tb(III)-GQ luminescence was proposed and evaluated. All performed tests confirmed interactions of MCs with studied GQ structure. Binding affinities of MCs were appreciable (KMC ~2-5×10(5)M(-1)). Higher concentration of MCs (the ratio of GQ:MC above 2.5) caused destabilization of tetraplex structure of GQ as evidenced by CD spectroscopy, melting temperatures, and Tb(III)-GQ luminescence quenching results.