Search Results (893)

Rare earth elements, comprising 17 elements including 15 lanthanides, are essential components in numerous high-tech applications. While physicochemical methods are commonly employed to remove toxic heavy metals (e.g., cadmium and mercury) from industrial wastewater, biological approaches offer increasingly attractive alternatives. Biomining, which utilizes microorganisms to extract valuable metals from ores and industrial wastes, and bioremediation, which leverages microorganisms to adsorb and transport metal ions into cells via active transport, provide eco-friendly solutions for resource recovery and environmental remediation. In this study, we investigated the potential of three recently identified lanthanide-binding proteins—SPL2, lanpepsy, and lanmodulin—for applications in these areas using single-cell inductively coupled plasma mass spectrometry (scICP-MS). Our results demonstrate that SPL2 exhibits superior characteristics for lanthanide and cadmium bioremediation. Heterologous expression of a cytosolic fragment of SPL2 in bacteria resulted in high expression levels and solubility. Single-cell ICP-MS analysis revealed that these recombinant bacteria accumulated lanthanum, cobalt, nickel, and cadmium, effectively sequestering lanthanum and cadmium from the culture media. Furthermore, SPL2 expression conferred enhanced bacterial tolerance to cadmium exposure. These findings establish SPL2 as a promising candidate for developing recombinant bacterial systems for heavy metal bioremediation and rare earth element biomining. Full article

In this paper, we investigate the magnetic exchange interaction and magnetization dynamics of two new members of the [LnRad(NO₃)₃] family, where Rad is a tripodal nitroxide, and Ln is Er(III) or Yb(III), having the prolate type electron density. Single OK crystal and powder X-ray diffraction studies showed that these complexes are isostructural with their previously investigated Y, Gd, Dy, Tm, Tb, Eu, and Lu congeners. A magnetometric investigation, supported by ab initio calculations, showed the presence of antiferromagnetic coupling between the lanthanide ion and the radical in both compounds with estimated J values of ≈7 and ≈20 cm⁻¹ for Er and Yb, respectively (+J S_eff∙ S formalism). Full article

Upconversion (UC) luminescence in doped lanthanide nanocrystals is associated with the energy migration (EM) process within clusters of dopant ions. The process of the synthesis of core–shell nanocrystals occurs at elevated temperatures, promoting the diffusion of the dopants into the shell accompanied by the decay of dopant clusters. The details of this unwanted effect are poorly understood. In this paper, we theoretically study a model of the diffusion of dopant ions in a nanocrystal using Monte Carlo (MC) simulations. We characterize the diffusion, spatial neighboring relations and clustering of dopant ions regarding the function of reduced temperature and MC time of the heating process. The dopants undergo a weak subdiffusion caused by trapping effects. The main results of this study are as follows: (i) the phase diagram of the variables reduced the temperature and MC time, which separates the enhanced and limited cluster-driven EM regimes, and (ii) a dependence of the average nearest distance between Yb ions as a function of reduced temperature, the concentration of Yb ions and MC time was found. In both cases, the requirements for an effective EM are formulated. Full article

Boosting the accuracy and speed of cancer detection is highly desirous in tumor detection, and sensors capable of detecting carcinoembryonic antigen (CEA) have great application prospects in this field. A highly sensitive sensor is constructed based on the fluorescence resonance energy transfer (FRET) with heavily rare-earth-doped upconversion nanoparticles (UCNPs) as energy donors and polydopamine nanoparticles (PDA NPs) as energy acceptors. This sensor detects the fluctuations in CEA molecules via luminescence quenching and recovery resulting from a competitive binding assay between CEA and PDA NPs. The high-level-doped design of UCNPs (i.e., NaYF₄@NaYbF₄:1%Tm@NaYF₄) is beneficial, providing upconversion luminescence intensity that is more than 10 times higher than that of the conventional low-level-doped UCNPs (i.e., NaYF₄@NaYF₄:20%Yb, 0.2%Tm@NaYF₄). The sensor exhibits impressive sensitivity. Specifically, in diluted fetal bovine serum, the detection limit reaches 0.013 ng/mL in the range of 0–1.5 ng/mL (S/N = 3), while the detection limit is 1.38 ng/mL in the range of 1.5–250 ng/mL (S/N = 3). This method has great potential for future applications in the rapid and early diagnosis and treatment of cancer. Full article

Pathogens and their metabolites in food present significant risks to both human health and economic development. Rising living standards and increasing awareness of food safety have driven the demand for sensitive and rapid detection methods. Lanthanide-doped upconversion nanoparticles (UCNPs), with their exceptional optical properties, have emerged as a promising platform for developing biosensors to detect pathogenic bacteria and their metabolites. The integration of UCNPs with point-of-care testing (POCT) has garnered considerable attention for its portability and immediacy, highlighting a promising future for biosensing, particularly in applications requiring quick and accurate diagnostics. This review explores the recognition elements and design principles commonly used in UCNP-based biosensors and examines various applications, including lateral flow assays, microfluidic systems, photoelectrochemical devices, and smartphone-integrated platforms. Despite significant advancements, challenges remain in the applicability and commercialization of UCNP-based biosensing technology. Future research should focus on enhancing sensitivity and specificity, developing scalable and cost-effective production methods, and integrating with advanced digital technologies to enable broader adoption. Addressing these challenges, establishing regulatory frameworks, and considering sustainability will be crucial to fully realizing the potential of UCNP-based biosensors. Full article

Although an increasing number of studies are being devoted to the field of corrosion, with topics from protection to sensing strategies, there is still a lack of research based on environmentally eco-friendly materials, which is essential in the transition to sustainable technologies. Herein, environmentally friendly composites, based on photoluminescent salts dispersed in vegetable oil-based resins, are prepared and investigated as corrosion sensing coatings. Two salts NaA, where A- is a lanthanide complex anion (with Ln = Nd³⁺, and Yb³⁺), are incorporated into the resins as active functional fillers and different coatings are prepared on carbon steel substrates to assess their functional properties. The influence exerted by a corrosive saline solution on the morphology, structural, and photoluminescent properties of the coatings is evaluated, and their suitability for the practical detection of the early corrosion of coated carbon steel is demonstrated. The photoluminescence of the composite coatings depends on the corrosion time, with the effect being more important for the coatings doped with Nd³⁺. The present work shows that the composites obtained are suitable candidates for corrosion sensing coating applications, offering improved sustainability. Full article

Lanthanides have seen rapid growth in the pharmaceutical and biomedical field, thus necessitating the development of hybrid metal–organic materials capable of exerting defined biological activities. Ternary hybrid lanthanide compounds were synthesized through reaction systems of Ln(III) (Ln = La, Nd, Eu) involving the antioxidant flavonoid chrysin (Chr) and 1,10-phenanhtroline (phen) under solvothermal conditions, thus leading to pure crystalline materials. The so-derived compounds were characterized physicochemically in the solid state through analytical (elemental analysis), spectroscopic (FT-IR, UV-visible, luminescence, ESI-MS, circular dichroism, ¹⁵¹Eu Mössbauer), magnetic susceptibility, and X-ray crystallographic techniques. The analytical and spectroscopic data corroborate the 3D structure of the mononuclear complex assemblies and are in line with theoretical calculations (Bond Valence Sum and Hirshfeld analysis), with their luminescence suggesting quenching on the flavonoid-phen electronic signature. Magnetic susceptibility data suggest potential correlations, which could be envisioned, supporting future functional sensors. At the biological level, the title compounds were investigated for their (a) ability to interact with bovine serum albumin and (b) antibacterial efficacy against Gram(−) (E. coli) and Gram(+) (S. aureus) bacteria, collectively revealing distinctly configured biological profiles and suggesting analogous applications in cellular (patho)physiologies. Full article

This work investigates nanostructured Ho_0.5Ca_0.5MnO₃, considered a model system of the Ln_0.5Ca_0.5MnO₃ series of manganites with perovskite structures featuring small lanthanide (Ln) ions half-substituted by Ca ions. Here, we propose a modified hybrid sol–gel–solid-state approach to produce multiple samples with a single batch, obtaining very high crystalline quality and ensuring the same chemical composition, with an average particle size in the range 39–135 nm modulated on-demand by a controlled calcination process. Our findings evidence that, provided the crystalline structure is preserved, the charge-ordering transition can be observed even at the nanoscale. Additionally, this research explores the presence of glassy phenomena, which are commonly seen in this class of materials, to enhance our understanding beyond simplistic qualitative observations. Comprehensive characterization using DC and AC magnetometry, along with relaxation and aging measurements, reveals that the complex dynamics typical of glassy phenomena emerge only at the nanoscale and are not visible in the bulk counterpart. Nevertheless, the analysis confirms that even the sample with the smallest nanoparticles cannot be intrinsically classified as canonical spin glass. Full article

A novel application of microresonators for refractometric sensing in aqueous media is presented. To carry out this approach, microspheres of different materials and sizes were fabricated and doped with Nd³⁺ ions. Under 532 nm excitation, the microspheres presented typical NIR Nd³⁺ emission bands with superimposed sharp peaks, related to the Whispering Gallery Modes (WGMs), due to the geometry of the microspheres. When the microspheres were submerged in water with increasing concentrations of glycerol, spectral shifts for the WGMs were observed as a function of the glycerol concentration. These spectral shifts were studied and calibrated for three different microspheres and validated with the theoretical shifts, obtained by solving the Helmholtz equations for the electromagnetic field, considering the geometry of the system, and also by calculating the extinction cross-section. WGM shifts strongly depend on the diameter of the microspheres and their refractive index (RI) difference compared with the external medium, and are greater for decreasing values of the diameter and lower values of RI difference. Experimental sensitivities ranging from 2.18 to 113.36 nm/RIU (refractive index unit) were obtained for different microspheres. Furthermore, reproducibility measurements were carried out, leading to a repeatability of 2.3 pm and a limit of detection of 5 × 10⁻⁴ RIU. The proposed sensors, taking advantage of confocal microscopy for excitation and detection, offer a robust, reliable, and contactless alternative for environmental water analysis. Full article

In recent years, the world scientific community has shown increasing interest in rare earth metals in general and their nanoparticles in particular. Medicine and pharmaceuticals are no exception in this matter. In this review, we have considered the main opportunities and potential applications of rare earth metal (gadolinium, europium, ytterbium, holmium, lutetium, dysprosium, erbium, terbium, thulium, scandium, yttrium, lanthanum, europium, neodymium, promethium, samarium, praseodymium, cerium) nanoparticles in biomedicine, with data ranging from single reports of effects found in vitro to numerous independent in vivo studies, as well as a number of challenges to their potential for wider application. The main areas of application of rare earth metals, including in the future, are diagnosis and treatment of malignant neoplasms, therapy of infections, as well as the use of antioxidant and regenerative properties of a number of nanoparticles. These applications are determined both by the properties of rare earth metal nanoparticles themselves and the need to search for new approaches to solve a number of urgent biomedical and public health problems. Oxide forms of lanthanides are most often used in biomedicine due to their greatest biocompatibility and nanoscale size, providing penetration through biological membranes. However, the existing contradictory or insufficient data on acute and chronic toxicity of lanthanides still make their widespread use difficult. There are various modification methods (addition of excipients, creation of nanocomposites, and changing the morphology of particles) that can reduce these effects. At the same time, despite the use of some representatives of lanthanides in clinical practice, further studies to establish the full range of pharmacological and toxic effects, as well as the search for approaches to modify nanoparticles remain relevant. Full article

Lanthanide molybdates are materials known for their mixed proton–ionic conductivity. This study investigates the effects of Pr content and Nb-doping on the crystal structure and electrical properties of the La_5.4−xPr_xMo_1−yNb_yO_12−δ (x = 0, 1.35, 2.7, 4.05, 5.4; y = 0, 0.1) series. The research focuses on two primary objectives: (i) enhancing the electronic conductivity through the use of Pr⁴⁺/Pr³⁺ redox pairs and (ii) increasing the ionic conductivity through Nb⁵⁺ aliovalent doping. The materials were thoroughly characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission and scanning electron microscopy (TEM and SEM), and complex impedance spectroscopy. The average crystal structure of the materials depended significantly on the Pr content. In general, compositions with a higher Pr content crystallize in a cubic fluorite-type structure, whereas those with a lower Pr content stabilize a rhombohedral polymorph. However, detailed TEM studies reveal a more complex local crystal structure characterized by nanodomains and incommensurate modulations. The highest conductivity values were observed in a N₂ atmosphere for compositions with an elevated Pr content, with values of 0.17 and 204.4 mS cm⁻¹ for x = 0 and x = 5.4, respectively, at 700 °C, which is attributed to electronic conduction mediated by the Pr⁴⁺/Pr³⁺ redox pair, as confirmed by XPS. These findings highlight the potential of tailored doping strategies to optimize the conducting properties of lanthanide molybdates for specific high-temperature electrochemical applications. Full article

Ratiometric lanthanide coordination polymers (Ln-CPs) are advanced materials that combine the unique optical properties of lanthanide ions (e.g., Eu³⁺, Tb³⁺, Ce³⁺) with the structural flexibility and tunability of coordination polymers. These materials are widely used in biological and chemical sensing, environmental monitoring, and medical diagnostics due to their narrow-band emission, long fluorescence lifetimes, and excellent resistance to photobleaching. This review focuses on the composition, sensing mechanisms, and applications of ratiometric Ln-CPs. The ratiometric fluorescence mechanism relies on two distinct emission bands, which provides a self-calibrating, reliable, and precise method for detection. The relative intensity ratio between these bands varies with the concentration of the target analyte, enabling real-time monitoring and minimizing environmental interference. This ratiometric approach is particularly suitable for detecting trace analytes and for use in complex environments where factors like background noise, temperature fluctuations, and light intensity variations may affect the results. Finally, we outline future research directions for improving the design and synthesis of ratiometric Ln-CPs, such as incorporating long-lifetime reference luminescent molecules, exploring near-infrared emission systems, and developing up-conversion or two-photon luminescent materials. Progress in these areas could significantly broaden the scope of ratiometric Ln-CP applications, especially in biosensing, environmental monitoring, and other advanced fields. Full article

A new compound [Y₂(sq)₃(H₂O)₄] (Y-sq; sq = squarate (C₄O₄^2–)) was prepared and structurally characterized. Since the RE-sq family (RE = Y, Dy, Yb, Lu) gave isostructural crystals, the objective of this study is to explore the effects of diamagnetic dilution on the SIM behavior through systematic investigation and comparison of diamagnetically diluted and undiluted forms. The 1%-Diluted Dy compounds, Dy@Y-sq and Dy@Lu-sq, showed AC magnetic susceptibility peaks without any DC bias field (H_DC), whereas undiluted Dy-sq showed no AC out-of-phase response under the same conditions. The Orbach and Raman mechanisms are assumed in the Arrhenius plots, giving U_eff/k_B = 139(5) and 135(8) K for Dy@Y-sq and Dy@Lu-sq, respectively, at H_DC = 0 Oe. In contrast, Yb@Y-sq and Yb@Lu-sq behaved different; Yb@Y-sq can be regarded as a field-induced SIM because AC out-of-phase response was recorded only when H_DC was present. On the other hand, Yb@Lu-sq showed a relaxation independent from temperature around 2 K at H_DC = 0 Oe, possibly ascribed to a quantum-tunneling-magnetization mechanism. Applying H_DC = 400 Oe afforded U_eff = 61.2(14) and 62.5(16) K for Yb@Y-sq and Yb@Lu-sq, respectively. The Y/Lu matrix dependence may be related to spin–phonon coupling. The dilution technique is a facile and versatile tool for modification of SIM characteristics. Full article

COx-free H₂, along with uniform carbon nanotubes, can be achieved together in high yield by CH₄ decomposition. It only needs a proper catalyst and reaction condition. Herein, Fe-based catalyst dispersed over titania-incorporated-alumina (Fe/Ti-Al), with the promotional addition of lanthanides, like CeO₂ and La₂O₃, over it, is investigated for a methane decomposition reaction at 800 °C with GHSV 6 L/(g·h) in a fixed-bed reactor. The catalysts are characterized by temperature-programmed reduction (TPR), powder X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy (TEM). The promoted catalysts are facilitated with higher surface area and enhanced dispersion and concentration of active sites, resulting in higher H₂ and carbon yields than unpromoted catalysts. Ceria-promoted 20Fe/Ti-Al catalyst had the highest concentration of active sites and always attained the highest activity in the initial hours. The 20Fe-2.5Ce/Ti-Al catalyst attains >90% CH₄ conversion, >80% H₂-yield, and 92% carbon yield up to 480 min time on stream. The carbon nanotube over this catalyst is highly uniform, consistent, and has the highest degree of crystallinity. The supremacy of ceria-promoted catalyst attained >90% CH₄ conversion even after the second cycle of regeneration studies (against 87% in lanthanum-promoted catalyst), up to 240 min time on stream. This study plots the path of achieving catalytic and carbon excellence over Fe-based catalysts through CH₄ decomposition. Full article

The multi-sublattice ferrimagnet Co₂FeO₂BO₃, a prominent example of lanthanide-free magnets, was the subject of element-selective studies using X-ray magnetic circular dichroism (XMCD) observations at the L- and K- X-ray absorption edges. Research findings indicate that the distinct magnetic characteristics of Co₂FeO₂BO₃, namely its remarkable high coercivity (which surpasses 7 Tesla at low temperatures), originate from an atypical arrangement of magnetic ions in the crystal structure (sp.gr. Pbam). The antiferromagnetic nature of the Co²⁺-O-Fe³⁺ exchange interaction was confirmed by identifying the spin and orbital contributions to the total magnetization from Co (m_L = 0.27 ± 0.1 μ_B/ion and m^eff_S = 0.53 ± 0.1 μ_B/ion) and Fe (m_L = 0.05 ± 0.1 μ_B/ion and m^eff_S = 0.80 ± 0.1 μ_B/ion) ions through element-selective XMCD analysis. Additionally, the research explicitly revealed that the strong magnetic anisotropy is a result of the significant unquenched orbital magnetic moment of Co, a feature that is also present in the related compound Co₃O₂BO₃. A complex magnetic structure in Co₂FeO₂BO₃, with infinite Co²⁺O₆ layers in the bc-plane and strong antiferromagnetic coupling through Fe³⁺ ions, is suggested by element-selective hysteresis data, which revealed that Co²⁺ ions contribute both antiferromagnetic and ferromagnetic components to the total magnetization. The findings underline the suitability of Co₂FeO₂BO₃ for applications in extreme environments, such as low temperatures and high magnetic fields, where its unique magnetic topology and anisotropy can be harnessed for advanced technologies, including materials for space exploration and quantum devices. This XMCD study opens the door to the production of novel high-coercivity, lanthanide-free magnetic materials by showing that targeted substitution at specific crystallographic sites can significantly enhance the magnetic properties of such materials. Full article