Dating the Paleolithic: Trapped charge methods and amino acid geochronology.

Despite the vast array of different geochronological tools available, dating the Paleolithic remains one of the discipline's greatest challenges. This review focuses on two different dating approaches: trapped charge and amino acid geochronology. While differing in their fundamental principles, both exploit time-dependent changes in signals found within crystals to generate a chronology for the material dated and hence, the associated deposits. Within each method, there is a diverse range of signals that can be analyzed, each covering different time ranges, applicable to different materials and suitable for different paleoenvironmental and archaeological contexts. This multiplicity of signals can at first sight appear confusing, but it is a fundamental strength of the techniques, allowing internal checks for consistency and providing more information than simply a chronology. For each technique, we present an overview of the basis for the time-dependent signals and the types of material that can be analyzed, with examples of their archaeological application, as well as their future potential.

Photo Luminescence and Radiative Carrier Losses in Monolayer Transition Metal Dichalcogenides.

The carrier losses due to radiative recombination in monolayer transition metal dichalcogenides are studied using fully microscopic many-body models. The density- and temperature-dependent losses in various Mo- and W-based materials are shown to be dominated by Coulomb correlations beyond the Hartree-Fock level. Despite the much stronger Coulomb interaction in 2D materials, the radiative losses are comparable-if not weaker-than in conventional III-V materials. A strong dependence on the dielectric environment is found in agreement with experimental results.

Boosting the Downconversion Luminescence of Tm3+-Doped Nanoparticles for S-Band Polymer Waveguide Amplifier.

Polymer waveguide devices have attracted increasing interest in several rapidly developing areas of broadband communications since they are easily adaptable to on-chip integration and promise low propagation losses. As a key member of the waveguide gain medium, lanthanide doped nanoparticles have been intensively studied to improve the downconversion luminescence. However, current research efforts are almost confined to erbium-doped nanoparticles and amplifiers operating at the C-band; boosting the downconversion luminescence of Tm3+ for S-band optical amplification still remains a challenge. Here we report a Tb3+-induced deactivation control to enhance Tm3+ downconversion luminescence in a stoichiometric Yb lattice without suffering from concentration quenching. We also demonstrate their potential application in an S-band waveguide amplifier and record a maximum optical gain of 18 dB at 1464 nm. Our findings provide valuable insights into the fundamental understanding of deactivation-controlled luminescence enhancement and open up a new avenue toward the development of an S-band polymer waveguide amplifier with high gain.

Behavior of Microstrain in Nd3+-Sensitized Near-Infrared Upconverting Core-Shell Nanocrystals for Defect-Induced Tailoring of Luminescence Intensity.

In an attempt to optimize the upconversion luminescence (UCL) output of a Nd3+-sensitized near-infrared (808 nm) upconverting core-shell (CS) nanocrystal through deliberate incorporation of lattice defects, a comprehensive analysis of microstrain both at the CS interface and within the core layer was performed using integral breadth calculation of high-energy synchrotron X-ray (λ = 0.568551 Å) diffraction. An atomic level interpretation of such microstrain was performed using pair distribution function analysis of the high-energy total scattering. The core NC developed compressive microstrain, which gradually transformed into tensile microstrain with the growth of the epitaxial shell. Such a reversal was rationalized in terms of a consistent negative lattice mismatch. Upon introduction of lattice defects into the CS systems upon incorporation of Li+, the corresponding UCL intensity was maximized at some specific Li+ incorporation, where the tensile microstrain of CS, compressive microstrain of the core, and atomic level disorders exhibited their respective extreme values irrespective of the activator ions.

Efficient Deep-Blue Light-Emitting Diodes from Highly Luminescent Eu2+-Doped Alkali Metal Halide Nanocrystals via Lattice Field Modulation.

Lead-halide perovskite nanocrystals (NCs) are promising for fabricating deep-blue (<460 nm) light-emitting diodes (LEDs), but their development is plagued by low electroluminescent performance and lead toxicity. Herein, the synthesis of 12 kinds of highly luminescent and eco-friendly deep-blue europium (Eu2+)-doped alkali-metal halides (AX:Eu2+; A = Na+, K+, Rb+, Cs+; X = Cl-, Br-, I-) NCs is reported. Through adjustment of the coordination environment, efficient deep-blue emission from Eu-5d → Eu-4f transitions is realized. The representative CsBr:Eu2+ NCs exhibit a high photoluminescence quantum yield of 91.1% at 441 nm with a color coordinate at (0.158, 0.023) matching with the Rec. 2020 blue specification. Electrically driven deep-blue LEDs from CsBr:Eu2+ NCs are demonstrated, achieving a record external quantum efficiency of 3.15% and half-lifetime of ∼1 h, surpassing the reported metal-halide deep-blue NCs-based LEDs. Importantly, large-area LEDs with an emitting area of 12.25 cm2 are realized with uniform emission, representing a milestone toward commercial display applications.

Jellyfish-Inspired Self-Healing Luminescent Elastomers Based on Borate Nanoassemblies for Dual-Model Encryption.

Responsive luminescent materials that reversibly react to external stimuli have emerged as prospective platforms for information encryption applications. Despite brilliant achievements, the existing fluorescent materials usually have low information density and experience inevitable information loss when subjected to mechanical damage. Here, inspired by the hierarchical nanostructure of fluorescent proteins in jellyfish, we propose a self-healable, photoresponsive luminescent elastomer based on dynamic interface-anchored borate nanoassemblies for smart dual-model encryption. The rigid cyclodextrin molecule restricts the movement of the guest fluorescent molecules, enabling long room-temperature phosphorescence (0.37 s) and excitation wavelength-responsive fluorescence. The building of reversible interfacial bonding between nanoassemblies and polymer matrix together with their nanoconfinement effect endows the nanocomposites with excellent mechanical performances (tensile strength of 15.8 MPa) and superior mechanical and functional recovery capacities after damage. Such supramolecular nanoassemblies with dynamic nanoconfinement and interfaces enable simultaneous material functionalization and self-healing, paving the way for the development of advanced functional materials.

Enabling Multimodal Luminescence in a Single Nanoparticle for X-ray Imaging Encryption and Anticounterfeiting.

Multimodal luminescent materials hold great promise in a diversity of frontier applications. However, achieving the multimodal responsive luminescence at the single nanoparticle level, especially besides light stimuli, has remained a challenge. Here, we report a conceptual model to realize multimodal luminescence by constructing both mechanoluminescence and photoluminescence in a single nanoparticle. We show that the lanthanide-doped fluoride nanoparticles are able to produce excellent mechanoluminescence through X-ray irradiation, and color-tunable mechanoluminescence becomes available by selecting suitable lanthanide emitters in a core-shell-shell structure. Furthermore, the design of a multilayer core-shell nanostructure enables multimodal emissions including radioluminescence, persistent luminescence, mechanoluminescence, upconversion, downshifting, and thermal-stimulated luminescence simultaneously in a single nanoparticle under multichannel excitation and stimuli. These results provide new insights into the mechanism of X-ray induced mechanoluminescence in nanocrystals and contribute to the development of smart luminescent materials toward X-ray imaging encryption, stress sensing, and anticounterfeiting.

Solution Synthesis and Light-Emitting Applications of One-Dimensional Lead-Free Cerium(III) Metal Halides.

Combining rare earth elements with the halide perovskite structure offers valuable insights into designing nonlead (Pb) luminescent materials. However, most of these compositions tend to form zero-dimensional (0D) networks of metal-halide polyhedra, with higher-dimensional (1D, 2D, and 3D) structures receiving relatively less exploration. Herein, we present synthesis and optical properties of Cs3CeCl6·3H2O, characterized by its unique 1D crystal structure. The conduction band minimum of Cs3CeCl6·3H2O becomes less localized as a result of the increased structural dimension, making it possible for the materials to achieve an efficient electrical injection. For both Cs3CeCl6·3H2O single crystals and nanocrystals, we also observed remarkable luminescence with near-unity photoluminescence quantum yield and exceptional phase stability. Cs3CeCl6·3H2O single crystals demonstrate an X-ray scintillation light yield of 31900 photons/MeV, higher than that of commercial LuAG:Ce (22000 photons/MeV); electrically driven light-emitting diodes fabricated with Cs3CeCl6·3H2O nanocrystals yield the characteristic emission of Ce3+, indicating their potential use in next-generation violet-light-emitting devices.

Metal Clusters Confined in Chiral Zeolitic Imidazolate Framework for Circularly Polarized-Luminescence Inks.

Chiroptical activities arising in nanoclusters (NCs) are emerging as one of the most dynamic areas of modern science. However, devising an overarching strategy that is capable of concurrently enhancing the photoluminescence (PL) and circularly polarized luminescence (CPL) of metal NCs remains a formidable challenge. Herein, gold and silver nanoclusters (AuNCs, AgNCs) are endowed with CPL, for the first time, through a universal host-guest approach─centered around perturbing a chiral microenvironment within chiral hosts, simultaneously enhancing emissions. Remarkably, the photoluminescence quantum yield (PLQY) of AuNCs has undergone an increase of over 200 times upon confinement, escalating from 0.05% to 12%, and demonstrates a CPL response. Moreover, a three-dimensional (3D) model termed "NCs@CMOF" featuring CPL activity is created using metal cluster-based assembly inks through the process of 3D printing. This work introduces a potentially straightforward and versatile approach for achieving both PL enhancement and CPL activities in metal clusters.

Lighting the way: how the Vibrio fischeri model microbe reveals the complexity of Earth's "simplest" life forms.

Vibrio (Aliivibrio) fischeri's initial rise to fame derived from its alluring production of blue-green light. Subsequent studies to probe the mechanisms underlying this bioluminescence helped the field discover the phenomenon now known as quorum sensing. Orthologs of quorum-sensing regulators (i.e., LuxR and LuxI) originally identified in V. fischeri were subsequently uncovered in a plethora of bacterial species, and analogous pathways were found in yet others. Over the past three decades, the study of this microbe has greatly expanded to probe the unique role of V. fischeri as the exclusive symbiont of the light organ of the Hawaiian bobtail squid, Euprymna scolopes. Buoyed by this optically amenable host and by persistent and insightful researchers who have applied novel and cross-disciplinary approaches, V. fischeri has developed into a robust model for microbe-host associations. It has contributed to our understanding of how bacteria experience and respond to specific, often fluxing environmental conditions and the mechanisms by which bacteria impact the development of their host. It has also deepened our understanding of numerous microbial processes such as motility and chemotaxis, biofilm formation and dispersal, and bacterial competition, and of the relevance of specific bacterial genes in the context of colonizing an animal host. Parallels in these processes between this symbiont and bacteria studied as pathogens are readily apparent, demonstrating functional conservation across diverse associations and permitting a reinterpretation of "pathogenesis." Collectively, these advances built a foundation for microbiome studies and have positioned V. fischeri to continue to expand the frontiers of our understanding of the microbial world inside animals.

luxA Gene From Enhygromyxa salina Encodes a Functional Homodimeric Luciferase.

Several clades of luminescent bacteria are known currently. They all contain similar lux operons, which include the genes luxA and luxB encoding a heterodimeric luciferase. The aldehyde oxygenation reaction is presumed to be catalyzed primarily by the subunit LuxA, whereas LuxB is required for efficiency and stability of the complex. Recently, genomic analysis identified a subset of bacterial species with rearranged lux operons lacking luxB. Here, we show that the product of the luxA gene from the reduced luxACDE operon of Enhygromyxa salina is luminescent upon addition of aldehydes both in vivo in Escherichia coli and in vitro. Overall, EsLuxA is much less bright compared with luciferases from Aliivibrio fischeri (AfLuxAB) and Photorhabdus luminescens (PlLuxAB), and most active with medium-chain C4-C9 aldehydes. Crystal structure of EsLuxA determined at the resolution of 2.71 Å reveals a (ß/α)8 TIM-barrel fold, characteristic for other bacterial luciferases, and the protein preferentially forms a dimer in solution. The mobile loop residues 264-293, which form a ß-hairpin or a coil in Vibrio harveyi LuxA, form α-helices in EsLuxA. Phylogenetic analysis shows EsLuxA and related proteins may be bacterial protoluciferases that arose prior to duplication of the luxA gene and its speciation to luxA and luxB in the previously described luminescent bacteria. Our work paves the way for the development of new bacterial luciferases that have an advantage of being encoded by a single gene.

Multimode Luminescence with Temperature and Energy Level Synergistic Dependence in Rare Earth Halide DPs for Advanced Multifunctional Applications.

Rare-earth halide double perovskites (DPs) have attracted extensive attention due to their excellent optoelectronic performance. However, the correlation between luminescence performance, crystal structure, and temperature, as well as the inherent energy transfer mechanism, is not well understood. Herein, Lanthanide ions (Ln3+: Nd3+ or Dy3+) as the co-dopants are incorporated into Sb3+ doped Cs2NaYbCl6 DPs to construct energy transfer (ET) models to reveal the effects of temperature and energy levels of rare earth on luminescence and ET. The different excited state structures of Sb3+-Ln3+ doped Cs2NaYbCl6 DPs at different temperatures and relative positions of energy levels of rare earth synergistically determine the physical processes of luminescence. These multi-mode luminescent materials exhibit good performance in anti-counterfeiting, NIR imaging, and temperature sensing. This work provides new physical insights into the effects of temperature and energy levels of rare earth on the energy transfer mechanism and related photophysical process.

Control of Luminescence and Interfacial Properties as Perspective for Upconversion Nanoparticles.

Near-infrared (NIR) light is highly suitable for studying biological systems due to its minimal scattering and lack of background fluorescence excitation, resulting in high signal-to-noise ratios. By combining NIR light with lanthanide-based upconversion nanoparticles (UCNPs), upconversion is used to generate UV or visible light within tissue. This remarkable property has gained significant research interest over the past two decades. Synthesis methods are developed to produce particles of various sizes, shapes, and complex core-shell architectures and new strategies are explored to optimize particle properties for specific bioapplications. The diverse photophysics of lanthanide ions offers extensive possibilities to tailor spectral characteristics by incorporating different ions and manipulating their arrangement within the nanocrystal. However, several challenges remain before UCNPs can be widely applied. Understanding the behavior of particle surfaces when exposed to complex biological environments is crucial. In applications where deep tissue penetration is required, such as photodynamic therapy and optogenetics, UCNPs show great potential as nanolamps. These nanoparticles can combine diagnostics and therapeutics in a minimally invasive, efficient manner, making them ideal upconversion probes. This article provides an overview of recent UCNP design trends, highlights past research achievements, and outlines potential future directions to bring upconversion research to the next level.

Dual Circularly Polarized Luminescence (CPL) and Piezoelectric Responses in Self-Assembled Chiral Nanostructures Derived from a Dipeptide Based Piezorganogel.

Next-generation medical and consumer electrical devices require soft, flexible materials. Piezoelectric materials, capable of converting mechanical stress into electrical energy, are of interest across various fields. Chiral nanostructures, with inherent chirality, have emerged as potential piezoelectric materials. Peptide-based materials, known for self-assembly and stimuli responsiveness, hold promise for the utilization of chiral nanostructures. When combined with luminescent chromophores, peptides can generate aggregation-induced chiroptical effects like Circularly Polarized Luminescence (CPL) and Circular Dichroism (CD). In this study, a chiral organogel, L,L-1 is synthesized, and its self-assembly, mechanical properties, and chiroptical features are examined. The organogel exhibits thermo-reversible and thixotropic behavior, forming fibrillar networks and 2D-sheets upon cooling. CD spectroscopy reveals aggregation-induced chirality on pyrene chromophore, resulting in CPL with glum values of 3.0 (± 0.2) × 10-3 and 3.1 (± 0.2) × 10-3 for L,L-1 and D,D-1, respectively. Notably, the 2D-sheets exhibit an enhanced piezoelectric response (d33 ≈76.0 pm V-1) compared to the fibrillar network (d33 ≈64.1 pm V-1). Introducing an electron-deficient molecule into the solution forms a Charge-transfer (CT) complex, modulating the piezoelectric response to d33 ≈52.44 pm V-1. This study offers a promising approach to optoelectronics design, presenting a chiral system with both CPL and piezoelectric responses, opening new possibilities for innovative applications.

Interfacing Lanthanide Metal-Organic Frameworks with ZnO Nanowires for Alternating Current Electroluminescence.

Alternating current electroluminescence (ACEL) devices are attractive candidates in cost-effective lighting, sensing, and flexible displays due to their uniform luminescence, stable performance, and outstanding deformability. However, ACEL devices have suffered from limited options for the light-emitting layer, which presents a significant constraint in the progress of utilizing ACEL. Herein, a new class of ACEL phosphors based on lanthanide metal-organic frameworks (Ln-MOFs) is devised. A synthesis of lanthanide-benzenetricarboxylate (Ln-BTC) thin film on a brass grid substrate seeded with ZnO nanowires (NWs) as anchors is developed. The as-synthesized Ln-BTC thin film is employed as the emissive layer and shows visible electroluminescence driven by alternating current (2.9 V µm-1 , 1 kHz) for the first time. Mechanistic investigations reveal that the Ln-based ACEL stems from impact excitation by accelerated electrons from ZnO NWs. Fine-tuning of the ACEL color is also demonstrated by controlling the Ln-MOF compositions and introducing an extra ZnS emitting layer. The advances in these optical materials expand the application of ACEL devices in anti-counterfeiting.

Achiral Solvent Inversed Helical Pathway and Cosolvent Controlled Excited-State "Majority Rule" in Enantiomeric Dansulfonamide Assemblies.

Achiral solvents are commonly utilized to induce the self-assembly of chiral molecules. This study demonstrates that achiral solvents can trigger helicity inversion in the assemblies of dansyl amphiphiles and control the excited-state "majority rule" in assemblies composed of pure enantiomers, through variation of the cosolvent ratio. Specifically, enantiomers of dansyl amphiphiles self-assemble into helical structures with opposite handedness in methanol (MeOH) and acetonitrile (MeCN), together with inversed circular dichroism and circularly polarized luminescence (CPL) signals. When a mixture of MeOH and MeCN is employed, the achiral cosolvents collectively affect the CPL of the assemblies in a way similar to that of "mixed enantiomers". The dominant cosolvent governs the CPL signal. As the cosolvent composition shifts from pure MeCN to MeOH, the CPL signals undergo a significant inversion and amplification, with two maxima observed at ≈20% MeOH and 20% MeCN. This study deepens the comprehension of how achiral solvents modulate helical nanostructures and their excited-state chiroptical properties.

Manipulating Chiroptical Activities in 0D Chiral Hybrid Manganese Bromides by Solvent Molecular Engineering.

0D hybrid metal halides (0D HMHs) with fully isolated inorganic units provide an ideal platform for studying the correlations between chiroptical activities and crystal structures at atomic levels. Here, through the incorporation of different solvent molecules, a series of 0D chiral manganese bromides (RR/SS-C20H28N2)3MnBr8·2X (X = C2H5OH, CH3OH, or H2O) are synthesized to elucidate their chiroptical properties. They show negligible circular dichroism signals of Mn absorptions due to C2v-symmetric [MnBr4]2- tetrahedra. However, they display distinct circularly polarized luminescence (CPL) signals with continuously increased luminescence asymmetry factors (glum) from 10-4 (X = C2H5OH) to 10-3 (X = H2O). The increased glum value is structurally revealed to originate from the enhancement of [MnBr4]2- tetrahedral bond-angle distortions, due to the presence of different solvent molecules. Furthermore, (RR/SS-C20H28N2)MnBr4·H2O enantiomers with larger bond-angle distortions of [MnBr4]2- tetrahedra are synthesized based on hydrobromic acid-induced structural transformation of (RR/SS-C20H28N2)3MnBr8·2H2O enantiomers. Therefore, such (RR/SS-C20H28N2)MnBr4·H2O enantiomers exhibit enhanced CPL signals with |glum| up to 1.23 × 10-2. This work provides unique insight into enhancing chiroptical activities in 0D HMH systems.

Color-Tunable Perovskite Nanomaterials with Intense Circularly Polarized Luminescence and Tailorable Compositions.

The ability to design halide perovskite nanocrystals (PNCs) with circularly polarized luminescence (CPL) offers exceptional potential in photonic technologies. Despite recent inspiring advances, the creation of PNCs with full-color tailorablity, outstanding CPL, and long-term stability remains a substantial challenge. Herein, a robust strategy to craft CPL-active PNCs is reported, exhibiting appealing full-color tunable wavelengths, enhanced CPL, and prolonged stability. In contrast to conventional methodologies, this strategy utilizes chiral nematic mesoporous silica (CNMS) as host to render in situ confined growth of diverse achiral PNCs. By strategically engineering photonic bandgap, adjusting loading amount of PNCs, and manipulating cations/anion compositions of PNCs, robust CPL responses with tunable wavelength and intensity are successfully obtained. The resulting PNCs-CNMS achieves stable CPL emissions with full-color tunability and impressive luminescent dissymmetric factors up to -0.17. Remarkably, silica-based hosts as a protective barrier confer exceptional resistance to humidity, photodegradation, and thermal stability, even up to 95 °C. Furthermore, the ability to achieve reversible CPL switching within PNCs-CNMS is attainable by leveraging the responsiveness of CNMS matrix or dynamic behavior of impregnated PNCs. Additionally, circularly polarized light-emitting diode devices based on PNCs-CNMS can be conveniently fabricated. This research affords a powerful platform for designing functional chiroptical materials.

Optical Properties Prediction for Red and Near-Infrared Emitting Carbon Dots Using Machine Learning.

Functional nanostructures build up a basis for the future materials and devices, providing a wide variety of functionalities, a possibility of designing bio-compatible nanoprobes, etc. However, development of new nanostructured materials via trial-and-error approach is obviously limited by laborious efforts on their syntheses, and the cost of materials and manpower. This is one of the reasons for an increasing interest in design and development of novel materials with required properties assisted by machine learning approaches. Here, the dataset on synthetic parameters and optical properties of one important class of light-emitting nanomaterials - carbon dots are collected, processed, and analyzed with optical transitions in the red and near-infrared spectral ranges. A model for prediction of spectral characteristics of these carbon dots based on multiple linear regression is established and verified by comparison of the predicted and experimentally observed optical properties of carbon dots synthesized in three different laboratories. Based on the analysis, the open-source code is provided to be used by researchers for the prediction of optical properties of carbon dots and their synthetic procedures.

InCl3-Assisted Surface Defects Restoring to Enhance Lead-Free Cs2ZrCl6 Nanocrystals for X-Ray Imaging and Blue LED Applications.

As one type of recent emerging lead-free perovskites, Cs2ZrCl6 nanocrystals are widely concerned, benefiting from the eminent designability, high X-ray cutoff efficiency, and favorable stability. Improving the luminescence performance of Cs2ZrCl6 nanocrystals has great importance to cater for practical applications. In view of the surface defects frequently formed by the liquid phase method, the particle morphology and surface quality of this material are expected to be regulated if certain intervention is made in the synthesis process. In the work, differing from normal cell lattice modulation based on the ion doping, the grain size and surface morphology of Cs2ZrCl6 nanocrystals are optimized via adding a certain amount of InCl3 to the synthetic solution. The surface defects are restored to inhibit the defect-induced non-radiative transition, resulting in the improvement of the luminescence properties. Moreover, a flexible Cs2ZrCl6@polydimethylsiloxane film with excellent heat, water, and bending resistance and a light-emitting diode (LED) device are fabricated, exhibiting excellent application potential for X-ray imaging and blue LED.