Search Results (990)

Upconverting nanoparticles, which transform low-energy infrared radiation into high-energy visible or UV light, show great potential in today’s technology. High-quality upconversion colloid (UCC) consisting of lanthanide-based nanoparticles with a diameter of ~10 nm was obtained using a combination of two processes: high-temperature coprecipitation and hydrothermal treatment in an autoclave. The UCC was then PEGylated with PEG-alendronate (PEG-Ale) to facilitate its dispersion in aqueous cell culture media intended for in vitro cell uptake assays. The surface modification of the nanoparticles increased both the colloidal stability in water and the upconversion emission by mitigating surface quenching. UCC@Ale-PEG was characterized by transmission and scanning electron microscopy, dynamic light scattering, and fluorescence microscopy detecting upconversion photoluminescence emission. The results of an in vitro assay revealed that this new generation of UCC can be internalized by various cell types, including epithelial cells and macrophages, upon several hours of exposure, suggesting broad application potential of this type of UCC in biomedicine, bioengineering, and environmental sciences. Full article

Erbium-165 (¹⁶⁵Er) is an Auger electron emitter with 7.2 electrons per decay and very few other emissions, making it an interesting candidate for Auger electron therapy. We present here a procedure for producing ¹⁶⁵Er by the ^natHo(p,n)¹⁶⁵Er nuclear reaction on a 16.5 MeV medical cyclotron. The target was prepared by pressing a Ho₂O₃:Al 1:1 (w/w) powder mixture on a Ag disc with a cylindrical depression in the center. With a 0.1 mm Nb foil in front, degrading the energy to 15 MeV, and water cooling at the back of the Ag disc, the target could withstand irradiation at currents up to 45 µA without showing any signs of damage. The beam tolerance of the target was also estimated by calculating the temperature and heat dissipation in the target via the numerical solution of the heat transport equations. For a 180 mg target, the production yield was 12.3 ± 1.9 MBq/µAh. The separation of two neighboring lanthanides is challenging, which led us to study the distribution coefficients for Er and Ho on commercially available LN2 resin for both HNO₃ and HCl eluents. Based on these values, we propose a purification procedure involving two successive LN2 columns for separating the ¹⁶⁵Er from Ho and Al, followed by a small TK221 column to concentrate the final eluate. No radionuclidic impurities were detected, and the chemical impurities found in the final formulation were traces of Ho, Er, Ca, Pb, and Fe. For three different chelators (DOTA, DTPA, and CHX-A″-DTPA), the effective molar activity of the final formulation was measured. The stability of the three complexes formed was also assessed upon incubation in mouse serum for 28 h. Full article

Plasmonic nanostructures have been widely employed to improve upconversion luminescence performance; however, their impact on excitation pathways under multi-wavelength excitation is not yet fully understood. In this work, we constructed hybrid systems composed of gold nanorod arrays and NaYF₄:Yb³⁺/Ln³⁺ (Ln = Er³⁺, Tm³⁺) upconversion nanoparticles to systematically investigate upconversion behavior under dual-wavelength excitation at 808 and 976 nm. Contrary to the expected synergistic enhancement, our experimental results demonstrate that dual-wavelength excitation in the plasmonic hybrid structures produces different responses of upconversion emission. Measurements dependent on excitation power, along with the analysis of emission intensity ratio, indicate that plasmonic coupling under dual-wavelength excitation significantly enhances dissipative pathways that compete with upconversion processes. Notably, these effects strongly depend on the intrinsic energy-level structure of the lanthanide ions. In the Er³⁺-doped system, excitation at 808 nm facilitates population of higher-lying excited states, but the overall upconversion gain remains limited. In contrast, in the Tm³⁺-doped system, plasmonic coupling markedly amplifies stimulated emission and cross-relaxation processes, causing rapid depletion of high-energy state populations and substantial suppression of luminescence. These findings elucidate the competition between upconversion and dissipation processes governing plasmon-assisted upconversion under dual-wavelength excitation and provide a physical foundation for manipulating upconversion luminescence using multiple wavelengths. Full article

The high reactivity of lanthanide metals poses a challenge to the electrochemical anodizing of surfaces for nanostructured coatings. This paper presents the first systematic experimental investigation of anodic oxidation of lanthanide gadolinium in aqueous solutions of citric, boric, oxalic, and tartaric acids. The voltage-current-time responses of anodizing of gadolinium, Al/Gd and Al/Nb/Gd systems were investigated. Anodic thin films were characterized using modern analysis techniques: SEM, FIB, and EDX. Morphology and voltage-current-time response analysis of anodized Al/Nb/Gd systems made it possible to establish the niobia cork-like effect and to develop a growth model. Full article

2,9-Bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen)-based ligands show great promise in the separation of trivalent lanthanides and actinides. Experimental studies have shown that americium forms stronger complexes with the BTPhen ligands than europium; most theoretical studies have so far failed to reproduce these results. In the current study, three different metal forms (the naked cation, its nitrate or perchlorate salts and tetraaqua solvated salts) were used to study different complexation reactions. It was shown that in the case of naked cations and salts, europium forms the most stable complex with the 2,9-bis(1,2-triazin-3-yl)-1,10-phenanthroline ligand in all of the reactions compared. However, europium is also more strongly interacting (compared to americium) with anions and water molecules in the tetraaquatrinitrato or tetraaquatriperchlorato complexes. That shifts the energies of reactions like Am(NO₃)₃·4H₂O + [Eu(H₂O)₄BTPhen]³⁺ = [Am(H₂O)₄BTPhen]³⁺ + Eu(NO₃)₃·4H₂O in favor of the americium being complexed with BTPhen and europium with anions and water. Therefore, the americium complexes with BTPhen become the more stable form, in an agreement with the experimental studies. Comparison of counterion influence (nitrate vs. perchlorate) indicates that bigger preference for americium over europium complexation corresponds to the nitrate complexes and stems mainly from the fact that in M(NO₃)₃(H₂O)₄ europium is stabilized more than in M(ClO₄)₃(H₂O)₄. Full article

Lanthanide ions and their complexes have emerged as versatile tools in biology and medicine owing to their unique photophysical, magnetic, and coordination properties. Their applications span bioimaging, sensing, therapy and diagnostics, underpinned by their strong preference for oxygen-donor ligands, kinetic stability, and tunable luminescence. This review integrates current developments in lanthanide coordination chemistry, focusing on the mechanistic basis of their interactions with biomolecules such as nucleic acids, proteins, and peptides. Moreover, this work highlights the design principles governing complex stability and biological compatibility, summarizing key biomedical uses of lanthanides ranging from imaging and drug delivery to anticancer and antioxidant effects, and discusses their toxicity and biodistribution, and their potential for clinical translation. In particular, this review offers a mechanistically oriented synthesis of recent advances, emphasizing the interplay between coordination behavior and biological function, and identifying emerging trends that define the current landscape of lanthanide-based bioinorganic research. By correlating molecular coordination features with biological performance, the review identifies the main trends shaping lanthanide-based bioinorganic research, also including a brief discussion of complexes formed between lanthanides and naturally occurring molecules, such as amino acids. Full article

Lanthanide-based single-molecule magnets are promising candidates for potential applications. Their magnetism is governed by ligand-field splittings, which may require up to 27 ligand-field parameters for accurate modeling. Determining these parameters reliably from measured data is a major challenge, for which machine learning approaches offer promising solutions. We provide an overview of these approaches and present our perspective on addressing the inverse problem relating experimental data to ligand-field parameters. Previously, a machine learning architecture combining a variational autoencoder (VAE) and an invertible neural network (INN) showed promise for analyzing temperature-dependent magnetic susceptibility data. In this work, the VAE-INN model is extended through data augmentation to enhance its tolerance to common experimental inaccuracies. Focusing on second-order ligand-field parameters, diamagnetic and molar-mass errors are incorporated by augmenting the training dataset with experimentally motivated error distributions. Tests on simulated experimental susceptibility curves demonstrate substantially improved prediction accuracy and robustness when the distributions correspond to realistic error ranges. When applied to the experimental susceptibility curve of the complex ${\mathrm{Al}}_2^{\mathrm{III}}$${\mathrm{Er}}_2^{\mathrm{III}}$, the augmented VAE–INN recovers ligand-field solutions consistent with least-squares benchmarks. The proposed data augmentation thus overcomes a key limitation, bringing the ML approach closer to practical use for higher-order ligand-field parameters. Full article

Lanthanide coordination polymers have been developed at a fast rate during the past two decades due to their appealing applications in the modern field of materials science and emerging technologies like luminescence, magnetism, sensing, gas adsorption, and catalysis. The role of lanthanides in imparting specific properties to the coordination polymers has been fully documented in extensive studies carried out by numerous research groups. It has been shown that because lanthanide(III) ions possess a variable coordination number, they readily build two-dimensional and three-dimensional architectures with definite channels, permanent pores, and distinct surface areas. Due to their strong oxophilic propensity and hard Lewis acid character, lanthanides favor the construction of stable coordination polymers and MOF configurations by strongly binding the coordinating groups of the organic linkers. Associated with palladium complexes, the lanthanide ions provide synergistic effects with Lewis acid sites, beneficial to the catalytic activity. These attractive characteristics of lanthanides enabled them to be fruitfully applied in Pd-Ln coordination polymers with catalytic properties. This review covers an array of Pd-Ln coordination polymers applied as heterogeneous catalysts in Suzuki–Miyaura C(sp²)-C(sp²) cross-coupling reactions. The activity and chemoselectivity of Pd(II) ions and Pd nanoparticles associated in coordination polymers with different lanthanides from a selected array of rare earth elements (Eu, Sm, Eu, Gd, Pr, Nd, Ce, La, or Tb) is discussed. High yields (>99%) are attained under optimized reaction conditions. The specific role of lanthanides and organic ligands in creating sustainable and recyclable heterogeneous Pd catalysts is evidenced. Mechanistic aspects of the C(sp²)-C(sp²) cross-coupling reactions are considered. The synergistic interaction between lanthanides and palladium as well as with the organic ligands is highlighted. Full article

Multicomponent mixed lanthanide oxide (MMLO) nanoparticles possess considerable potential as multimodal imaging agents because they integrate diverse excellent optical and magnetic properties within a single nanoparticle. Herein, we present triply and quadruply mixed lanthanide oxide nanoparticles, namely, gadolinium (Gd)/dysprosium (Dy)/europium (Eu) oxide (GDEO), Gd/Dy/terbium (Tb) oxide (GDTO), and Gd/Dy/Eu/Tb oxide (GDETO) nanoparticles. Gd³⁺ can strongly induce positive (T₁) contrast in magnetic resonance imaging (MRI), Dy³⁺ and Tb³⁺ can generate negative (T₂) contrast in MRI, and Eu³⁺ and Tb³⁺ emit visible photons that are applicable to fluorescence imaging (FI). All the nanoparticles were grafted with hydrophilic, biocompatible polyacrylic acid (PAA) to enhance colloidal stability and biocompatibility and further grafted with small amounts of an organic photosensitizer, 2,6-pyridinedicarboxylic acid (PDA), to obtain a high absolute fluorescent quantum yield (QY) with an extended fluorescent lifetime (τ). All PAA-MMLO and PAA/PDA-MMLO nanoparticles exhibited nearly monodispersed particle-size distributions with average particle diameters of ~2 nm and displayed considerably higher longitudinal (r₁) and transverse (r₂) water proton spin relaxivities than commercial molecular MRI contrast agents. The PAA/PDA-GDEO, PAA/PDA-GDTO, and PAA/PDA-GDETO nanoparticles exhibited high absolute QYs of 45, 29, and 61%, respectively, and long τ values of 1–2 ms, making them suitable for time-delayed noise-free fluorescence signal detection. These findings confirm the high potential of PAA-MMLO nanoparticles as T₁ and/or T₂ MRI contrast agents and PAA/PDA-MMLO nanoparticles as both T₁ and/or T₂ MRI and FI agents. Full article

The escalating prevalence of counterfeiting and forgery has imposed unprecedented demands on advanced anti-counterfeiting technologies. Traditional luminescent materials, relying on single-mode or static emission, are inherently vulnerable to replication using commercially available phosphors or simple spectral blending. Multimode luminescent materials exhibiting excitation wavelength-dependent emission offer significantly higher encoding capacity and forgery resistance. Herein, we report the colloidal synthesis of lanthanide-doped Cs₂ZrCl₆ nanocrystals (Ln³⁺ = Tb, Eu, Pr, Sm, Dy, Ho) via a robust hot-injection route. These nanocrystals universally exhibit efficient host-to-guest energy transfer from self-trapped excitons (STEs) under 254 nm, yielding sharp characteristic Ln³⁺ f–f emission alongside the intrinsic broadband STE luminescence. Critically, Tb³⁺ enables direct 4f → 5d excitation at ~275 nm, while Eu³⁺ introduces a low-energy Eu³⁺ ← Cl⁻ LMCT band at ~305 nm, completely bypassing STE emission. Due to their multimode luminescent characteristics, we fabricate a triple-mode anti-counterfeiting label displaying different colors under different types of excitation. These findings establish a breakthrough excitation-encoded multimode platform, offering potential applications for next-generation photonic security labels, scintillation detectors, and solid-state lighting applications. Full article

Radiotherapy, a cornerstone of cancer treatment, is critically limited by tumor radioresistance and off-target toxicity. Lanthanide-based nanomaterials (Ln-NPs) have recently emerged as a versatile and promising class of theranostic radiosensitizers to overcome these hurdles. This review comprehensively outlines the state-of-the-art in Ln-NP-enabled radiotherapy, beginning with their fundamental physicochemical properties and synthesis and then delving into the multi-level mechanisms of radiosensitization, including high-Z element-mediated physical dose amplification, catalytic generation of reactive oxygen species (ROS), and disruption of DNA damage repair pathways. The unique capacity of certain Ln-NPs to serve as MRI contrast agents is highlighted as the foundation for image-guided, dose-painting radiotherapy. We critically summarize the preclinical and clinical progress of representative systems, benchmarking them against other high-Z nanomaterials. Finally, this work discusses the ongoing challenges, such as biocompatibility, targeted delivery, and regulatory hurdles, and envisages future directions, including combinatorial strategies with immunotherapy and the development of personalized nanotheranostic paradigms. Through this synthesis, this review aims to provide a clear roadmap for the continued development and clinical integration of lanthanide nanotheranostics in oncology. Full article

Low-temperature Ag₂Se is a narrow-band semiconductor, with its transport and optical properties significantly influenced by the local coordination environment. This study investigates the effects of La and Gd incorporation using DFT+U calculations and Ag-K edge EXAFS analysis. Analysis of electron localization function (ELF) and charge density differences reveals increased electron localization at dopant sites. Additionally, k³χ(k) and wavelet transforms demonstrate that the first M-Se shell shifts from approximately 1.346 Å in Ag-Se to around 1.386 Å and 1.291 Å for La-Se and Gd-Se, respectively (phase-uncorrected), thereby confirming dopant-specific lattice distortions while maintaining the orthorhombic framework. The observed changes are associated with an increase in dielectric strength, with ε₂ increasing from approximately 30–40 in pristine Ag₂Se to around 50–60 for La and 70–80 for Gd at low photon energies, alongside enhanced absorption nearing 1.32–1.34 × 10⁵ cm⁻¹. The characteristic plasmon resonance in the range of 15–20 eV is maintained. Rare-earth substitution effectively adjusts local bonding and low-energy optical response in Ag₂Se, with Gd demonstrating the most significant impact among the examined dopants. Full article

Divalent europium complexes have attracted significant attention in various fields due to the unique electronic configuration of the Eu(II) ion. Given the high sensitivity of the 5d → 4f emission of Eu(II) ions to the ligand field, it is crucial to explore the relationship between ligands and this emission in Eu(II) complexes. However, the heavy-atom effects on the 5d → 4f emission of Eu(II) complexes coordinated with non-metal elements in the same group remain unclear. In this study, five mononuclear Eu(II)-chalcogenide complexes, Eu[H₃B·EPh-κE,H,H]₂(DME)₂ (E = S for 1 and Se for 2; DME = 1,2-Dimethoxyethane) and Eu[EPh]₂(18-C-6) (E = S for 3, Se for 4, and Te for 5; 18-C-6 = 1,4,7,10,13,16-Hexaoxacyclooctadecane), were synthesized via reduction of diphenyl disulfide chalcogenide analogs with Eu(BH₄)₂(THF)₂ or NaH. The structures of these complexes were investigated by single-crystal X-ray diffraction, and their properties were characterized by thermogravimetric analysis and photophysical property tests. Complexes 1 and 2 are isomorphous and show similar yellowish-green luminescence, while complexes 3–5 have similar structures but crystallize in different space groups with bluish-green luminescence. This research reveals the influence of chalcogenide ligands on the 5d → 4f emission of Eu(II) complexes, providing a theoretical basis and new research ideas for the application of Eu(II) complexes in various fields, including luminescent materials, cryogenic refrigerants, and magnetic materials. Full article

With the discovery of amorphous oxide semiconductors, a new era of electronics opened. Indium gallium zinc oxide (IGZO) overcame the problems of amorphous and poly-silicon by reaching mobilities of ~10 cm²/Vs and demonstrating thin-film transistors (TFTs) are easy to manufacture on transparent and flexible substrates. However, mobilities over 30 cm²/Vs have been difficult to reach and other materials have been introduced. Recently, polycrystalline In₂O₃ has demonstrated breakthroughs in the field. In₂O₃ TFTs have attracted attention because of their high mobility of over 100 cm²/Vs, which has been achieved multiple times, and because of their use in scaled devices with channel lengths down to 10 nm for high integration in back-end-of-the-line (BEOL) applications and others. The present review focuses first on the material properties with the understanding of the bandgap value, the importance of the position of the charge neutrality level (CNL), the doping effect of various atoms (Zr, Ge, Mo, Ti, Sn, or H) on the carrier concentration, the optical properties, the effective mass, and the mobility. We introduce the effects of the non-parabolicity of the conduction band and how to assess them. We also introduce ways to evaluate the CNL position (usually at ~E_C + 0.4 eV). Then, we describe TFTs’ general properties and parameters, like the field effect mobility, the subthreshold swing, the measurements necessary to assess the TFT stability through positive and negative bias temperature stress, and the negative bias illumination stress (NBIS), to finally introduce In₂O₃ TFTs. Then, we will introduce vacuum and non-vacuum processes like spin-coating and liquid metal printing. We will introduce the various dopants and their applications, from mobility and crystal size improvements with H to NBIS improvements with lanthanides. We will also discuss the importance of device engineering, introducing how to choose the passivation layer, the source and drain, the gate insulator, the substrate, but also the possibility of advanced engineering by introducing the use of dual gate and 2 DEG devices on the mobility improvement. Finally, we will introduce the recent breakthroughs where In₂O₃ TFTs are integrated in neuromorphic applications and 3D integration. Full article

This study focuses on improving the operational properties of a magnesium potassium phosphate (MPP) matrix MgKPO₄ × 6H₂O for the immobilization of radioactive waste (RW) by introducing detonation nanodiamonds (NDs). The study evaluates the impact of NDs on the phase composition of the resulting composite based on the MPP matrix (further referred to as MPP-ND composite), as well as its compressive and flexural strength, porosity, thermal conductivity, and leaching resistance to actinides (²³⁹Pu, ²³⁸U) and europium (as a lanthanide simulator). It was found that the optimal content of NDs in the composite is 1 wt%, along with 20 wt% of wollastonite as a reinforcing additive. This MPP-ND composite exhibited high compressive and flexural strengths of 24 and 4 MPa, respectively, a thermal conductivity coefficient of (0.5–1.0) W/(m∙K) in the interval of (47–510) °C, and a minimal open porosity of no more than 5%. An increase in hydrolytic stability to leaching of actinides and europium due to their prior sorption on NDs was observed. The leaching rates of ²³⁹Pu, ²³⁸U, and Eu from the MPP-ND composite on the 28th day of sample contact with water were 3.5 × 10⁻⁶, 1.5 × 10⁻⁴, and 4.0 × 10⁻⁶ g/(cm²·day), respectively. Thus, for the first time, data on the influence of NDs on the physicochemical properties and hydrolytic stability of MPP-ND composite demonstrating the practical applicability of this composite for RW immobilization have been obtained. Full article