Luminescent Lanthanide Research Articles

Dual–resonance enhancement and polarization control of upconversion luminescence of NaYF4:Yb,Er nanoparticles on 2D metal gratings

In this work, we report enhancement and polarization control of multi–color (green/red) upconversion luminescence (UCL) of lanthanide–doped (NaYF4:Yb,Er) nanoparticles by dual–resonance modes of surface plasmons (SP) on two–dimensional (2D) metal gratings in orthogonal directions. Investigations are performed for the SP resonance modes to be tuned, by adjusting the grating periods, to match any one or two of the green–UCL, red–UCL and excitation wavelengths. It is shown that, for the upconversion nanoparticles (UCNPs) on the 2D gratings with both of the dual resonance modes matching the green–/red–UCL or excitation wavelength, enhancements of the UCLs are roughly doubled, compared with their one–dimensional (1D) counterparts. And when the dual resonance modes match the green– or red–UCL and the excitation wavelength, enhancements of the UCLs are further greatly improved, in spite that the resonance modes for the excitation and emission light are in orthogonal directions. As the emitted UCL photons are largely coupled with the dual SP resonance modes, the radiated green– and red–UCL light can be distinguished by their linear polarization states in orthogonal directions. It is also indicated that polarization of the excitation light can influence the polarization of the UCL light when coupled with the SP resonance modes.

A luminescent lanthanide functionalized hydrogen-bonded organic framework hydrogel: Fluorescence sensing platform for copper and iron ions detection

A luminescent lanthanide functionalized hydrogen-bonded organic framework hydrogel: Fluorescence sensing platform for copper and iron ions detection

Strong Red Luminescence in Europium Complexes Solution for Anti-Counterfeiting Applications.

Eu3+-activated phosphors with distinct photoluminescence properties are well-suited for diverse applications, including lighting, sensing, and imaging. Despite their potential, the large-scale and energy-efficient production of Eu3+-doped phosphors remains a significant challenge for industrial applications. This research delves into the luminescent performance of Eu3+ ions in nitrate solutions at room temperature by employing detailed spectroscopic characterization. Results reveal vibrant red luminescence at 594 nm and 616 nm in europium nitrate solutions, irrespective of concentration or solvent. We proposed a luminescent mechanism based on the formation of coordination complexes in nitrate solution. Furthermore, the investigation highlights the superior performance of NH2- over CH2-ligands in mitigating the deactivation of Eu3+ emissive state induced by OH- oscillators in H2O solvent, leading to enhanced photoluminescence. Particularly, europium nitrate solutions without lengthy preparation exhibit ligand-dependent luminescent feature, showcasing potential applications in anti-counterfeiting and coordination group structure detection. This study here not only enhances our understanding of rare earth luminescence mechanisms, but also broadens the range of rare earth luminescent materials.

Luminescent rare earth complexes of Ce3+, Eu2+and Yb2+with spiro-bis(pyrazolyl)borate ligands containing C–H···M interactions

Luminescent rare earth complexes based on interconfigurational 5d-4f transition have characteristics of adjustable emission spectra and short excited state lifetimes, showing potential applications in display, lighting and other fields. In this work, nine Ce3+, Eu2+ and Yb2+ complexes with spiro-bis(pyrazolyl)borate ligands, where pyrazolyl stands for pyrazolyl, 3-methylpyrazolyl, or 3,5-dimethylpyrazolyl, were designed and synthesized. Ce3+ complexes show emission colors of blue, with photoluminescence quantum yields (PLQYs) of 94%–100%; Eu2+ complexes show emission colors of yellow-green, with PLQYs of 60%–78%; Yb2+ complexes show emission colors of orange or red, with PLQYs of 3%–4%. In addition, the crystal structures and theoretical calculation results show C–H···M interactions between bridge-head H atoms of the spirane and central metal ions in these complexes. It is found that the introduction of spirane with large steric hindrance and the existence of C–H···M interactions can improve the stability of the complexes in air atmosphere.

Elucidating Polyphosphate Anion Binding to Lanthanide Complexes Using EXAFS and Pulsed EPR Spectroscopy.

Reversible anion binding to lanthanide complexes in aqueous solution has emerged as an effective method for anion sensing. Through careful design of the organic ligand, luminescent lanthanide complexes capable of binding biologically relevant anions in a bidentate or monodentate manner can be realized. While single-crystal X-ray diffraction analyses and NMR spectroscopy have revealed the structural geometry of several host-guest complexes, the challenge remains in designing preorganized lanthanide receptors with enhanced anion selectivity for broader applications in diagnostics and bioimaging. To address this challenge, innovative and complementary methods to investigate host-anion binding geometry are becoming increasingly important. Herein, we demonstrate the combined use of Eu L3-edge extended X-ray absorption fine structure (EXAFS) and electron paramagnetic resonance (EPR) spectroscopy to elucidate the binding of nucleoside phosphates (ATP, ADP, and AMP) to a cationic lanthanide complex. We establish that ATP unequivocally binds the lanthanide center in a bidentate manner in water, while ADP adopts both bidentate and monodentate modes, and AMP binds in a monodentate manner. This interdisciplinary approach provides deeper insight into lanthanide host-guest chemistry in solution, laying the groundwork for designing emissive probes that undergo specific anion-induced structural changes and elicit desired optical responses upon binding.

Regulating Energy Transfer Pathways to Construct Multicolor Luminescent Lanthanide Metal–Organic Frameworks and Their Multiorder Anticounterfeiting Barcodes and Antibiotic Sensing

Regulating Energy Transfer Pathways to Construct Multicolor Luminescent Lanthanide Metal–Organic Frameworks and Their Multiorder Anticounterfeiting Barcodes and Antibiotic Sensing

Green syntheses of novel luminescent lanthanide compounds based on pentafluorobenzoate

Green syntheses employing aqueous solutions of lanthanide chloride, NaOH, and pentafluorobenzoic acid were successfully developed and produced pure dinuclear α-Ln compounds, [Ln(L)3(H2O)4]2·2H2O (L: pentafluorobenzoate) and new ones: η-Ln, Na[Ln(L)3(H2O)4]·L·2H2O, and θ-Ln, with Ln: Eu(III), Gd(III), and Tb(III). The synthesis becomes even greener when mechanochemistry is employed because it is quantitative, solvent-free, fast (30 min), and energy efficient. The θ-Ln compounds still have unknown composition and structure, so its description and properties are not explored. The η-Ln compounds are 1-D coordination polymer with only one bridging L, which leads to a large Ln···Ln distance (6.865 Å). Heteronuclear α-Ln0.50Ln0.50′ and η-LnxLn1−x′ compounds, with x = 0.05, 0.25, 0.50, and 0.75, Ln, Ln′: Eu, Tb, and Gd, have been synthesized by mixing the proper proportion of the lanthanide chlorides in the initial solution. The η-EuxTb1−x materials present Tb(III) → Eu(III) energy transfer, which confers interesting luminescent and photophysical properties with relevant potential applications. The color of the emission under UV irradiation can be tuned by the composition of the η-EuxTb1−x materials as well as by the excitation wavelength. In addition, it was observed a significant increase (ca. 35–260 %) of the D05 Eu(III) emission lifetime in the η-EuxTb1−x compounds by varying the excitation wavelength.

Micronuclear battery based on a coalescent energy transducer.

Micronuclear batteries harness energy from the radioactive decay of radioisotopes to generate electricity on a small scale, typically in the nanowatt or microwatt range1,2. Contrary to chemical batteries, the longevity of a micronuclear battery is tied to the half-life of the used radioisotope, enabling operational lifetimes that can span several decades3. Furthermore, the radioactive decay remains unaffected by environmental factors such as temperature, pressure and magnetic fields, making the micronuclear battery an enduring and reliable power source in scenarios in which conventional batteries prove impractical or challenging to replace4. Common radioisotopes of americium (241Am and 243Am) are α-decay emitters with half-lives longer than hundreds of years. Severe self-adsorption in traditional architectures of micronuclear batteries impedes high-efficiency α-decay energy conversion, making the development of α-radioisotope micronuclear batteries challenging5,6. Here we propose a micronuclear battery architecture that includes a coalescent energy transducer by incorporating 243Am into a luminescent lanthanide coordination polymer. This couples radioisotopes with energy transducers at the molecular level, resulting in an 8,000-fold enhancement in energy conversion efficiency from α decay energy to sustained autoluminescence compared with that of conventional architectures. When implemented in conjunction with a photovoltaic cell that translates autoluminescence into electricity, a new type of radiophotovoltaic micronuclear battery with a total power conversion efficiency of 0.889% and a power per activity of 139 microwatts per curie (μW Ci-1) is obtained.

Upconversion and NIR-II luminescent rare earth nanoparticles combined with machine learning for cancer theranostics.

How to develop contrast agents for cancer theranostics is a meaningful and challenging endeavor, and rare earth nanoparticles (RENPs) may provide a possible solution. In this study, we initially modified RENPs through the application of photodynamic agents (ZnPc) and targeted the bevacizumab antibody for cancer theranostics, which was aimed at improving the therapeutic targeting and efficacy. Subsequently, we amalgamated anthocyanin with the modified RENPs, creating a potential cancer diagnosis platform. When the spectral data were obtained from the composite of cells, the crucial information was extracted through a competitive adaptive reweighted sampling feature algorithm. Then, we employed a machine learning classification model and classified both the individual spectral data and fused spectral data to accurately predict distinctions between breast cancer and normal tissue. The results indicate that the amalgamation of fusion techniques with machine learning algorithms provides highly precise predictions for molecular-level breast cancer detection. Finally, in vitro and in vivo experiments were carried out to validate the near-infrared luminescence and therapeutic effectiveness of the modified nanomedicine. This research not only underscores the targeted effects of nanomedicine but also demonstrates the potent synergy between optical spectral technology and machine learning. This innovative approach offers a comprehensive strategy for the integrated treatment of breast cancer.

Harnessing Spatiotemporal-Specific Tumorous Exosome Dynamics: Ultra-Sensitive Lanthanide Luminescence Detection Strategy Enabled by Exosomal Membrane Engineering for Melanoma Immunotherapy Monitoring.

Focused on the newly secreted tumorous exosomes during melanoma immunotherapy, this work has pioneered an ultra-sensitive spatiotemporal-specific exosome detection strategy, leveraging advanced exosomal membrane engineering techniques. The proposed strategy harnesses the power of amplified lanthanide luminescence signals on these exosomes, enabling precise and real-time monitoring of the efficacy of melanoma immunotherapy. The methodology comprises two pivotal steps. Initially, Ac4ManNAz-associated metabolic labeling is employed to evolve azide groups onto the membranes of newly secreted exosomes with remarkable selectivity. These azide groups serve as versatile clickable artificial tags, enabling the precise identification of melanoma exosomes emerging during immunotherapy. Subsequently, lanthanide-nanoparticle-functionalized polymer chains are controllably grafted onto the exosome surfaces through click chemistry and in situ Fenton-RAFT polymerization, serving as robust signal amplifiers. When integrated with time-resolved fluorescence detection, this strategy yields detection signals with an exceptionally high signal-to-noise ratio, enabling ultra-sensitive detection of PD-L1 antigen expression levels on the spatiotemporal-specific exosomes. The detection strategy boasts a wide linear concentration range spanning from 1.7 × 104 to 1.7 × 109 particles/mL, with a remarkable theoretical detection limit of 1.28 × 103 particles/mL. The remarkable enhancements in detection sensitivity and accuracy facilitate the evaluation of the efficacy of immunotherapeutic interventions in the mouse B16 melanoma model, notably revealing a substantial disparity in PD-L1 levels between immunotherapy-treated and untreated groups (P < 0.01) and further emphasizing the cumulative therapeutic effect that intensifies with repeated treatments (P < 0.001).

Efficient photosensitized luminescence from Eu3+ in inert nanocrystals via ligand coordination

Abstract Luminescent lanthanide ions incorporated in sodium yttrium fluoride nanocrystals are promising as new luminescent materials in optoelectronics and bioimaging since the nonradiative transition is significantly suppressed due to the absence of high-energy vibrational modes. To prepare optically and electrically active nanocrystals, we explored organic ligands that allow efficient triplet energy transfer to Eu3+ incorporated into nanocrystals, resulting in an efficient photosensitization effect in colloidal solutions and films. Further, we applied these emitting nanocrystals to light-emitting devices and observed the electroluminescence.

Efficient broadband near-infrared emission based on copper-alloyed metal halides

Recently, metal halides have shown broad application prospects due to excellent electronic and optical properties. Although significant developments have been realized, the spectra range of their photoluminescence (PL) emission is mainly limited to the visible region. Near-infrared (NIR) emitting materials are widely used in the fields of night vision, biomedical imaging, non-destructive food inspection, etc. On this occasion, extending the luminescence scope of metal halides to NIR region is of great significance. Generally, NIR-emitted metal halides are realized through rare earth (RE) ions doping. However, RE luminescence usually have narrow-band characteristics, which makes it difficult to realize broadband NIR emission. In this study, we present an efficient broadband NIR-emitted metal halide CsAgBr2 through copper ions alloying, its emission locates at 830 nm with a large FWHM (full width at half maximum) of 332 nm. Theoretical calculations suggest that the incorporation of Cu+ could effectively modulate the density of states and enhance the localized characterization, which is beneficial to boost the PL efficiency. Furthermore, this material displays favorable structure stability under ambient conditions. This study demonstrates the great application potential of Cu+-alloyed CsAgBr2 in the field of NIR optical electronics.

Unusually Large Ligand Field Splitting in Anionic Europium(III) Complexes Induced by a Small Imidazolic Counterion.

Luminescent trivalent lanthanide (Ln3+) complexes are compounds of technological interest due to their unique photophysical properties, particularly anionic tetrakis complexes, given their higher stability and emission quantum yields. However, structural studies on the cation-anion interaction in these complexes and the relation of such to luminescence are still lacking. Herein, the cation-anion interactions in two luminescent anionic tetrakis(2-thenoyltrifluoroacetonato)europate(III) complexes with alkylimidazolium cations, specifically 1-ethyl-3-methylimidazolium and 1-butyl-3-methylimidazolium are investigated. The Eu3+ complexes were synthesized and characterized by elemental analysis, mass spectrometry, and single-crystal X-ray crystallography, and their luminescence spectra were recorded at 77 K. Quantum chemical calculations were also performed. X-ray crystallography revealed hydrogen bonds between the enolate ligands and imidazolium ring hydrogens. The 1-butyl-3-methylimidazolium complex had two crystallographic Eu3+ sites, also confirmed by luminescence spectroscopy. The 1-ethyl-3-methylimidazolium complex exhibited an unusual 300 cm-1 splitting in the 5D0 → 7F1 transition, as reproduced by ligand field calculations, suggesting a stronger hydrogen bonding due to the smaller substituent. We hypothesize that this strong bonding likely causes angular distortions, resulting in high ligand field splittings.

Facile Synthesis of Ln-Doped Hydrogen-Bonded Organic Frameworks with Rare-Earth-Characteristic Long Persistent Luminescence.

Tunable luminescence-assisted information storage and encryption holds increasing significance in today's society. A promising approach to incorporating the benefits of both organic long persistent luminescent (LPL) materials and rare-earth (RE) luminescence lies in utilizing organic host materials to sensitize RE luminescence, as well as hydrogen-bonded organic framework (HOF) phosphorescence Förster resonance energy transfer to RE compound luminescence. This work introduces a one-pot, in situ pyrolytic condensation method, achieved through high-temperature melting calcination, to synthesize lanthanide ion-doped HOF materials. This method circumvents the drawback of molecular triplet energy annihilation, enabling the creation of organic LPL materials with RE characteristics. The HOF material serves as the host, exhibiting blue phosphorescence and cyan LPL. By fine-tuning the doping amount, the composite material U-Tb-100 achieves green LPL with a luminescent quantum yield of 56.4%, and an LPL duration of approximately 2-3 s, demonstrating tunable persistence. Single-crystal X-ray diffraction, spectral analysis, and theoretical calculation unveil that U-Tb-100 exhibits exceptional quantum yield and long-lived luminescence primarily due to the efficient sensitization of U monomer to RE ions and the PRET process between U and RE complexes. This ingenious strategy not only expands the repertoire of HOF materials but also facilitates the design of multifunctional LPL materials.

Maximizing Nanoscale Downshifting Energy Transfer in a Metallosupramolecular Cr(III)-Er(III) Assembly.

Pseudo-octahedral CrIIIN6 chromophores hold a unique appeal for low-energy sensitization of NIR lanthanide luminescence due to their exceptionally long-lived spin-flip excited states. This allure persists despite the obstacles and complexities involved in integrating both elements into a metallosupramolecular assembly. In this work, we have designed a structurally optimized heteroleptic CrIII building block capable of binding rare earths. Following a complex-as-ligand synthetic strategy, two heterometallic supramolecular assemblies, in which three peripherical CrIII sensitizers coordinated through a molecular wire to a central ErIII or YIII, have been prepared. Upon excitation of the CrIII spin-flip states, the downshifted Er(4I13/2 → 4I15/2) emission at 1550 nm was induced through intramolecular energy transfer. Time-resolved experiments at room temperature reveal a CrIII → ErIII energy transfer of 62-73% efficiencies with rate constants of about 8.5 × 105 s-1 despite the long donor-acceptor distance (circa 14 Å). This efficient directional intermetallic energy transfer can be rationalized using the Dexter formalism, which is promoted by a rigid linear electron-rich alkyne bridge that acts as a molecular wire connecting the CrIII and ErIII ions.

High-sensitivity luminescent temperature sensors: MFX:1%Sm2+ (M = Sr, Ba, X = Cl, Br).

The use of lanthanide luminescence has advanced the field of remote temperature sensing. Luminescence intensity ratio methods relying on emission from two thermally coupled energy levels are popular but suffer from a limited temperature range. Here, we present a versatile luminescent thermometer: Ba(Sr)FBr(Cl):Sm2+. The Sm2+ ion benefits from multiple thermally coupled excited states to extend the temperature range and has strong parity-allowed 4f6→4f55d1 absorption to increase brightness. We conduct a comparative analysis of the temperature sensing performance of Sm2+ in BaFBr, BaFCl, SrFBr, and SrFCl and address the role of concentration, host, and Boltzmann equilibration. Different thermal coupling schemes, 5D1-5D0 and 4f55d1-5D0, and temperature-dependent lifetimes enable accurate sensing between 350 and 800 kelvin. Differences in 4f55d1-5D0 energy gap allows optimization for a temperature range of interest. This type of Sm2+-based thermometer holds great potential for temperature monitoring in the wide and relevant range up to 500°C.

(Invited) Near-Infrared Triggered Theranostics

In the last decade, the field of luminescent lanthanide doped nanoparticles has had a meteoric rise, progressing from the basic understanding of the photophysical properties governing their nanoscale luminescence, in particular upconversion, to their use in a plethora of applications, with considerable focus in biology and medicine. This interest stems primarily from the ability to stimulate these luminescent nanoparticles with near-infrared (NIR) light as well as their diverse emission wavelengths spanning the UV to the NIR. Therefore, with a single NIR excitation wavelength, it is possible to observe higher energy multiphoton luminescence, known as upconversion, or single photon NIR emission (known as down-shifted luminescence). The former upconversion process proceeds through the sequential absorption of multiple NIR photons through the long-lived 4f electronic energy states of the tri-positive lanthanide ions. As a result, upconversion is several of orders more efficient than conventional multiphoton absorption processes. This is especially interesting for applications in theranostics (therapy + diagnostics on the same platform) where the upconverted light can be used to trigger another light activated modality (therapy) while the NIR luminescence can be used for bioimaging and nanothermometry (diagnostics). Here, we present our work on the synthesis and development of various NIR excited (and emitting) core/shell lanthanide-doped nanostructures/nanoplatforms and demonstrate how their various emissions could be harnessed for applications in biology and nanomedicine.

Up-Conversion Luminescence and Optical Temperature Sensing Properties of NaLuF4:Yb3+/Ho3+ Micron-Sized Crystals at Low Temperature.

Non-contact temperature sensors utilising the fluorescence intensity ratio and the unique up-conversion (UC) luminescence of rare-earth ions have numerous benefits; however, their operational temperature range has remained limited. In this study, NaLuF4:Yb3+/Ho3+ samples were prepared by the hydrothermal method. The samples exhibited exceptional UC luminescence properties at low temperatures. The intensity of the green emission (with peak wavelengths of 540 and 546 nm) gradually decreased with increasing temperature, and the green emissions showed a unique change at low temperatures. In addition, we studied the dependence of the UC luminescence intensity on the excitation power and the variation in the decay lifetime with temperature. The experiments revealed excellent luminous performance and significantly enhanced sensitivity at low temperatures; the maximum absolute sensitivity Sa and relative sensitivity Sr of the 540 and 546 nm thermally coupled energy levels were 1.02% and 0.55% K-1, respectively. The potential temperature sensing properties of Yb3+/Ho3+-co-doped NaLuF4 makes it suitable for temperature sensing applications at temperatures as low as 30 K. This study offers a novel approach for the advancement of temperature sensing technology at low temperatures.

Modulating Visible-Light Driven NIR Lanthanide Polymer Photocatalysis for Amplification Detection of Exosomal Proteins and Cancer Diagnosis.

Near-infrared (NIR) luminescent lanthanide materials hold great promise for bioanalysis, as they have anti-interference properties. The approach of efficient luminescence is sensitization through a reasonable chromophore to overcome the obstacle of the aqueous phase. The involvement of the surfactant motif is an innovative strategy to arrange the amphiphilic groups to be regularly distributed near the polymer to form a closed sensitized space. Herein, a lanthanide polymer (TCPP-PEI70K-FITC@Yb/SDBS) is designed in which the meso-tetra(4-carboxyphenyl)porphine (TCPP) ligand serves as both a sensitizer and photocatalytic switch. The surfactant sodium dodecyl benzenesulfonate (SDBS) wraps the photosensitive polymers to form a hydrophobic layer, which augments the light-harvesting ability and expedites its photocatalysis. TCPP-PEI70K-FITC@Yb/SDBS is subsequently applied as an amplified photocatalysis toolbox for universally regulating the generation of reactive oxygen species (ROS). Boosting 3,3',5,5'-tetramethylbenzidine (TMB) oxidation to produce blue products, a dual-mode biosensor is fabricated for improving the diagnosis of programmed death ligand-1-positive (PDL1) cancer exosomes. Exosomes were captured by Fe3O4 modified by the PDL1 aptamer, enabling replacement of alkaline phosphatase (ALP)-labeled multiple hybridized chains; then, the isolated ALP triggered a hydrolysis reaction to block the generation of oxTMB. Detection sensitivity improves by 1 order of magnitude through SDBS modulation, down to 104 particles/mL. The sensor performed well clinically in distinguishing cancer patients from healthy individuals, expanding physiological applications of near-infrared lanthanide luminescence.

Thermal stability and luminescence of zinc and lanthanide(Tb3+ and Ce3+) coordination polymers with pyridine-2,5-dicarboxylic acid by the WASSR method

Two sorts of inorganic-organic coordination polymers (Tb2Zn(2,5-PDC)4・10H2O(I), Ce2Zn2(2,5-PDC)5・2H2O(II))constructed by lanthanide(TbIII 、CeIII) and ligand of the pyridine-2,5-dicarboxylate have been prepared by the soft chemical synthesis method(WASSR method). The purpose of this study was to investigate optic property, thermal stability and dehydration/hydration behavior. The experimental results indicated Tb compound(I) show stronger red phosphor than Ce compound(II), but framework of crystal structure is weaker than Ce compound(II) on account of XRD patterns comparison between dehydrated compound and re-hydrated compound. The thermal stability of Ce compound(II) is better than Tb compound(I) owing to the first weight loss temperature is high to Tb compound about 200 °C.