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A photon avalanche (PA) effect that occurs in lanthanide-doped solids gives rise to a giant nonlinear response in the luminescence intensity to the excitation light intensity. As a result, much weaker lasers are needed to evoke such PAs than for other nonlinear optical processes. Photon avalanches are mostly restricted to bulk materials and conventionally rely on sophisticated excitation schemes, specific for each individual system. Here we show a universal strategy, based on a migrating photon avalanche (MPA) mechanism, to generate huge optical nonlinearities from various lanthanide emitters located in multilayer core/shell nanostructrues. The core of the MPA nanoparticle, composed of Yb 3+ and Pr 3+ ions, activates avalanche looping cycles, where PAs are synchronously achieved for both Yb 3+ and Pr 3+ ions under 852 nm laser excitation. These nanocrystals exhibit a 26th-order nonlinearity and a clear pumping threshold of 60 kW cm −2 . In addition, we demonstrate that the avalanching Yb 3+ ions can migrate their optical nonlinear response to other emitters (for example, Ho 3+ and Tm 3+ ) located in the outer shell layer, resulting in an even higher-order nonlinearity (up to the 46th for Tm 3+ ) due to further cascading multiplicative effects. Our strategy therefore provides a facile route to achieve giant optical nonlinearity in different emitters. Finally, we also demonstrate applicability of MPA emitters to bioimaging, achieving a lateral resolution of ~62 nm using one low-power 852 nm continuous-wave laser beam. A general mechanism, migrating photon avalanche, can generate large optical nonlinearity from various lanthanides emitters at the nanoscale.

The Ca2+-sensing protein calmodulin (CaM) is a popular model of biological ion binding since it is both experimentally tractable and essential to survival in all eukaryotic cells. CaM modulates hundreds of target proteins and is sensitive to complex patterns of Ca2+ exposure, indicating that it functions as a sophisticated dynamic transducer rather than a simple on/off switch. Many details of this transduction function are not well understood. Fourier transform infrared (FTIR) spectroscopy, ultrafast 2D infrared (2D IR) spectroscopy, and electronic structure calculations were used to probe interactions between bound metal ions (Ca2+ and several trivalent lanthanide ions) and the carboxylate groups in CaM’s EF-hand ion-coordinating sites. Since Tb3+ is commonly used as a luminescent Ca2+ analog in studies of protein−ion binding, it is important to characterize distinctions between the coordination of Ca2+ and the lanthanides in CaM. Although functional assays indicate that Tb3+ fully activates many Ca2+-dependent proteins, our FTIR spectra indicate that Tb3+, La3+, and Lu3+ disrupt the bidentate coordination geometry characteristic of the CaM binding sites’ strongly conserved position 12 glutamate residue. The 2D IR spectra indicate that, relative to the Ca2+-bound form, lanthanide-bound CaM exhibits greater conformational flexibility and larger structural fluctuations within its binding sites. Time-dependent 2D IR lineshapes indicate that binding sites in Ca2+−CaM occupy well-defined configurations, whereas binding sites in lanthanide-bound-CaM are more disordered. Overall, the results show that binding to lanthanide ions significantly alters the conformation and dynamics of CaM’s binding sites.

Lanthanide hydrogels HGLn with iminodiacetic acid (Ln = Eu and Gd) and Na [Ln(DPA) ]·9H O complexes (DPA = dipicolininate) were successfully synthesized via hydrothermal microwave-assisted and via precipitation, respectively. Incorporation of Ln(DPA) complexes into the HGLn hydrogels resulted in the improvement of the spectroscopic properties and mechanical behavior. Rheological studies of the europium hydrogels doped with Gd(DPA) complex (HGEu-Gd) showed a significant increase in the stiffness of the material by increasing the concentration of the incorporated complex. This effect also influences the increase in luminescence intensity of the HGEu-Gd hybrid. A computational modeling study of the interaction between the complex and hydrogel matrix suggests that this interaction does not affect the coordination symmetry of either Eu or Gd . On the other hand, there were changes in the corresponding emission lifetimes, although not accompanied by changes in the emission spectral profile. The individual contributions to the luminescence of the hybrid gel were related to the maintenance of individual material characteristics and those resulting from hydrogel-complex interactions.

Heptanuclear GdIII7 (complex 1) and tetradecanuclear GdIII14 (complex 2) were synthesized using the rhodamine 6G ligand HL (rhodamine 6G salicylaldehyde hydrazone) and characterized. Complex 1 has a rare disc-shaped structure, where the central Gd ion is connected to the six peripheral GdIII ions via CH3O−/μ3-OH− bridges. Complex 2 has an unexpected three-layer double sandwich structure with a rare μ6-O2− ion in the center of the cluster. Magnetic studies revealed that complex 1 exhibits a magnetic entropy change of 17.4 J kg−1 K−1 at 3 K and 5 T. On the other hand, complex 2 shows a higher magnetic entropy change of 22.3 J kg−1 K−1 at 2 K and 5 T.

De novo protein design has succeeded in generating a large variety of globular proteins, but the construction of protein scaffolds with cavities that could accommodate large signaling molecules, cofactors, and substrates remains an outstanding challenge. The long, often flexible loops that form such cavities in many natural proteins are difficult to precisely program and thus challenging for computational protein design. Here we describe an alternative approach to this problem. We fused two stable proteins with C2 symmetry—a de novo designed dimeric ferredoxin fold and a de novo designed TIM barrel—such that their symmetry axes are aligned to create scaffolds with large cavities that can serve as binding pockets or enzymatic reaction chambers. The crystal structures of two such designs confirm the presence of a 420 cubic Ångström chamber defined by the top of the designed TIM barrel and the bottom of the ferredoxin dimer. We functionalized the scaffold by installing a metal-binding site consisting of four glutamate residues close to the symmetry axis. The protein binds lanthanide ions with very high affinity as demonstrated by tryptophan-enhanced terbium luminescence. This approach can be extended to other metals and cofactors, making this scaffold a modular platform for the design of binding proteins and biocatalysts.

The advent of chemical tools for cellular imaging--from organic dyes to green fluorescent proteins--has revolutionized the fields of molecular biology and biochemistry. Lanthanide-based probes are a new player in this area, as the last decade has seen the emergence of the first responsive luminescent lanthanide probes specifically intended for imaging cellular processes. The potential of these probes is still undervalued by the scientific community. Indeed, this class of probes offers several advantages over organic dyes and fluorescent proteins. Their very long luminescence lifetimes enable quantitative spatial determination of the intracellular concentration of an analyte through time-gating measurements. Their emission bands are very narrow and do not overlap, enabling the simultaneous use of multiple lanthanide probes to quantitatively detect several analytes without cross-interference. Herein we describe the principles behind the development of this class of probes. Sensors for a desired analyte can be designed by rationally manipulating the parameters that influence the luminescence of lanthanide complexes. We will discuss sensors based on varying the number of inner-sphere water molecules, the distance separating the antenna from the lanthanide ion, the energies of excited states of the antenna, and PeT switches.

The first reference on this rapidly growing topic provides an essential up-to-date guide to current and emerging trends.A group of international experts has been carefully selected by the editors to cover all the central aspects, with a focus on molecular species while also including industrial applications.

Lanthanide‐doped upconversion nanoparticles (UCNPs) exhibit unique luminescence properties, making them promising for applications in displays, sensors, security labels, and solar cells. Embedding UCNPs in polymer films can enhance their functionality; however, the properties of the polymer matrix significantly influence the dispersion and loading capacity of UCNPs, ultimately affecting optical performance. In this study, we investigate the incorporation of UCNPs into two distinct polymer matrices, poly(3‐hexylthiophene) (P3HT) and poly(methyl methacrylate) (PMMA), via spin coating at different speeds. Our findings demonstrate that UCNP dispersion and monodispersity are governed by polymer polarity, viscosity, and UCNP concentration in the suspension. To enhance UCNP loading, multiple spin coatings were explored. In UCNP−P3HT films, the volume fraction of UCNPs increased from 26.1% to 51.4% after three consecutive spin coatings, while maintaining a uniform distribution. In contrast, the lower miscibility and higher viscosity of PMMA restricted UCNP loading to 12.0% before significant clustering occurred. Although multiple spin coatings increased the total UCNP content in PMMA films, the volume fraction decreased to 8.0% due to film thickening. This comparative analysis highlights the critical role of polymer matrix properties in UCNP embedding and provides valuable insights for optimizing UCNP−polymer composites for advanced optical applications. We study the fabrication of nanocomposite thin films incorporating upconversion nanoparticles into two types of polymer matrices, demonstrating the key roles of nanoparticle surface–polymer compatibility and processing conditions in determining particle dispersity and loading capacity.

In this investigation, we explore the integration of lanthanides into Metal–Organic Frameworks (MOFs) to enable Near-Infrared (NIR) emission. Specifically, we focus on Lanthanide-Naphthalene Dicarboxylate based MOFs (Ln-MOFs), incorporating elements such as Praseodymium (Pr), Samarium (Sm), Dysprosium (Dy), and Erbium (Er). The synthesis of Ln-MOFs is achieved via the hydrothermal method. The structure, morphology, thermal stability, and luminescence properties of synthesized Ln-MOFs have been evaluated through different characterization techniques. Upon photoexcitation at 350 nm, Ln-MOFs show the emission in the Visible and NIR region. Further, the luminescence intensity of Ln-MOFs enhanced by 2–3 folds in the visible region and 6–8 folds in NIR region after exposing to Gamma irradiation at 150 kGy. Cytotoxic effect on the viability of MDA-MB 231 and MDA-MB 468 Triple negative breast cancer (TNBC) cells was evaluated by MTT assay. The results revealed that among all synthesized MOFs, Pr-MOF exhibited an aggressive cytotoxic effect. Additionally, analysis of phase-contrast microscopy data indicates that Pr-MOF induces alterations in the morphology of both MDA-MB 231 and MDA-MB 468 TNBC cells when compared to untreated controls. The findings in this study reveal the utilization of Ln-MOFs for studying cytotoxicity and highlight their ability to enhance near-infrared (NIR) emission when exposed to gamma radiation.

The use of luminescence in biological systems allows one to diagnose diseases and understand cellular processes. Molecular systems, particularly lanthanide(III) complexes, have emerged as an attractive system for application in cellular luminescence imaging due to their long emission lifetimes, high brightness, possibility of controlling the spectroscopic properties at the molecular level, and tailoring of the ligand structure that adds sensing and therapeutic capabilities. This review aims to provide a background in luminescence imaging and lanthanide spectroscopy and discuss selected examples from the recent literature on lanthanide(III) luminescent complexes in cellular luminescence imaging, published in the period 2016–2020. Finally, the challenges and future directions that are pointing for the development of compounds that are capable of executing multiple functions and the use of light in regions where tissues and cells have low absorption will be discussed.