Luminescent Species Research Articles

Identification and Quantification of Multiphase U(VI) Speciation on Gibbsite with pH Using TRLFS and PARAFAC of Excitation Emission Matrices.

The significant abundance of uranium in radioactive waste inventories worldwide necessitates a thorough understanding of its behavior. In this work, the speciation of uranyl(VI), (UO22+) in a gibbsite system under ambient conditions has been determined as a function of pH by deconvolution and analysis of luminescence spectroscopic data. Uniquely, a combined experimental and statistical approach utilizing time-resolved luminescence spectroscopy and parallel factor analysis (PARAFAC) of excitation emission matrices has been successfully utilized to identify four separate luminescent U(VI) species in the uranyl-gibbsite system for the first time. The speciation of all luminescent U(VI) species in an environmentally relevant system over a pH range of 6-11 is discerned through the analysis of emission fingerprints at low temperature (20 K). Comparison of the deconvoluted luminescence spectra with mineral standards and geochemical models of the system allows the assignment of the luminescent chemical species as metaschoepite, Na-compreignacite, surface adsorbed ≡AlO2-UO2(OH) and ≡AlO2-UO2(CO3)24- complexes, with assignments supported by fitting of extended X-ray absorption fine structure data. The combined spectroscopic techniques in this study show that assignment and quantification of uranyl(VI) species in a sorption system over a large pH range can be accurately achieved using PARAFAC to deconvolute a three way emission spectroscopic data set.

Carbon Dot Synthesis in CYTOP Optical Fiber Using IR Femtosecond Laser Direct Writing and Its Luminescence Properties.

Luminescent carbon dots (CDs) were locally synthesized in the core of CYTOP fibers using IR femtosecond laser direct writing (FLDW), a one-step simple method serving as a post-treatment of the pristine fiber. This approach enables the creation of several types of modifications such as ellipsoid voids. The CDs and photoluminescence (PL) distribute at the periphery of the voids. The PL spectral properties were studied through the excitation/emission matrix in the visible range and excitation/emission spectra in the UV/visible range. Our findings reveal the presence of at least three distinct luminescent species, facilitating a broad excitation range extending from UV to green, and light emission spanning from blue to red. The average laser power and dose influence the quantity and ratio of these luminescent CD species. Additionally, we measured the spatially resolved lifetime of the luminescence during and after the irradiation. We found longer lifetimes at the periphery of the laser-induced modified regions and shorter ones closer to the center, with a dominant lifetime ~2 ns. Notably, unlike many other luminophores, these laser-induced CDs are insensitive to oxygen, enhancing their potential for display or data storage applications.

Recent Developments in Halide Perovskite Nanocrystals for Indirect X‐ray Detection

AbstractMetal halide perovskites are revolutionizing X‐ray detection through a combination of low cost, solution processing, favorable optoelectronic properties, and high stopping power for high‐energy ionizing radiation. While perovskite single crystals and polycrystalline wafers are considered direct X‐ray converters, most medical X‐ray applications are based on scintillators that shift high‐energy radiation into the visible. Several materials are on the market, but demonstrations based on CsPbBr3 nanocrystals, possibly embedded in a matrix material or combined with organic molecules as luminescent species, highlight their competitiveness with established scintillators in terms of radioluminescence yield and transient behavior. Major hurdles that perovskite nanocrystal scintillators must overcome are environmental stability and toxicity. While there are still few examples of high‐performance lead‐free perovskite nanocrystal scintillators, microcrystalline perovskites are emerging with promising properties, reduced toxicity, and significant Stokes shifts to avoid reabsorption of emission in thick films. Thus, the near future of perovskite nanocrystal scintillator materials will primarily be the adoption of recipes for materials with proven properties in microcrystalline form. The nanocrystal colloidal solutions will facilitate the large‐scale printing of homogeneous and scattering‐free films to obtain high contrast and spatial resolution X‐ray images by scintillation.

Meticulously designed red emission carbon dots as efficient and stable luminescent species for rapid latent fingerprint recognition and light emitting diodes

The preparation of carbon dots (CDs) emitting long wavelength has attracted more attentions due to their unique advantages in biological and optoelectronic fields, including the wide absorption, long PL lifetime and deep-tissue penetration. Herein, we prepare the nitrogen and sulfur co-doped red emission carbon dots (R-CDs) from the 2,4-diaminodiphenylamine (DDA) and thiourea via a solvothermal reaction, which exhibit reliable red emission at 613 nm and possess a high quantum yield (QY) of 34 %. Meanwhile, the structural analysis and theoretical calculation reveal that the sulfur doping from thiourea increases the nitrogen and oxygen content of CDs, leading to the red emission observed in R-CDs. Subsequently, we design an integrated fingerprints recognition system based on the R-CDs phosphors for the imaging of latent fingerprints (LFPs) and fast LFPs recognition, expanding the application of biometric identification and comparison technology based on fluorescence. Finally, we successfully apply the R-CDs into red and white light-emitting diodes, improving plant growth efficiency. As a result, this work provides a new in-depth insight of red emission CDs and expands the application in latent fingerprint recognition and light-emitting diodes.

Hydrogen‐Bonded Organic Frameworks as an Appealing Platform for Luminescent Sensing

AbstractHydrogen‐bonded organic frameworks (HOFs), a novel subclass of porous crystalline materials self‐assembled from organic linkers through hydrogen bonding and other intermolecular interactions, have emerged as an exciting platform for developing multifunctional materials. Recently, luminescent HOF sensors have drawn considerable attention due to their unique advantages, such as hydrogen‐bonding flexibility, inherent luminescent centers in organic linkers, ease of functionalization, low density and toxicity, and good stability. However, a comprehensive study on the design strategies, functionalities, and applications of HOFs in sensing is lacking. In this review, the uniqueness and development of luminescent sensing HOFs are outlined. The design principles and strategies to enable the sensing performance are summarized, including the pre‐design of luminescent organic linkers and post‐modification with additional luminescent species. The state‐of‐the‐art advances in diverse sensing applications are overviewed, such as the detection of chemical pollutants, biomolecules, gases, and physical factors like temperature and mechanical forces. Moreover, the current challenges and corresponding potential avenues are discussed. This review aims to inspire more innovative research on the fabrication of advanced HOFs for luminescent sensing functions.

Ag(I) Ion-Concentration-Dependent Dynamic Mechanism of Thiolactic-Acid-Capped Gold Nanoclusters Revealed by Fluorescence Spectra and Two-Dimensional Correlation Spectroscopy.

Based on fluorescence spectroscopy, being combined with several spectral analysis techniques including principal component analysis (PCA), two-dimensional correlation spectroscopy (2D-COS), and moving window 2D-COS, the study disclosed the structural variations of gold nanoclusters capped by thiolactic acid (AuNCs@TLA) induced by Ag(I) ions. Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) were applied to monitor the morphology evolution of the surface and composition of the nanoclusters induced by Ag(I) ions. Several spectral components, centered at (790, 607) nm, (670, 590) nm, and (740, 670) nm were revealed by 2D-COS analysis, suggesting new luminescent species or groups were generated with the introduction of Ag(I) ions. A two-stage mechanism was revealed for the photoluminescence variations of AuNCs@TLA induced by Ag(I) ion. The first stage was characterized by the emission quench of 790 nm followed by the emerging emission of 607 nm, which was attributed to the anti-galvanic reaction; and the second stage featured by the noticeable growth of the emission's intensity around 670 nm as result of the AuNCs' size effect. The present study will attract more focuses on near-infrared (NIR)-emitted metal nanoclusters and promote their synthesis and utilities.

Silicon solar cell efficiency improvement employing electrostatically assembled polyelectrolyte–quantum dot multilayers

Down-shifting (DS) has proven to be an effective technique to address thermalization losses in photovoltaic devices. It involves the modification of the incident solar spectrum by luminescent species to better suit solar cell’s optimal absorption regions. Despite the number of favorable characteristics of quantum dots (QDs) as DS materials, their incorporation into highly ordered close-packed films remains the major drawback of QD-based DS applications. This limitation can be overcome by the sequential integration of QDs into a multilayered film via the layer-by-layer assembly technique, that allows the precise control of composition and thickness. The experimental results discussed herein indicate that upon optimization employing a model-assisted design approach, the spectral response of a silicon solar cell benefits from the down-shifting and antireflection capabilities of the QD film, as evinced by their quantum efficiency. For the optimum design, the incorporation of QDs triggered an increment of 26.1% in the power conversion efficiency driven by an increase of 29.2% in the short circuit current density. The controlled assembly of QD multilayers offers unique opportunities in light harvesting for new hybrid photovoltaic technologies.

Expanding Luminescence Horizons in Macropolyhedral Heteroboranes

AbstractLuminescence is observed in three novel macropolyhedral nineteen‐ and eighteen‐vertex chalcogenaboranes: Se2B17H17 (1), SeB17H19 (3) and SeB18H20 (4). This led us to the recognition that previously published macropolyhedral heteroborane species might also exhibit luminescence. Thus, the known nineteen‐ and eighteen‐vertex dithiaboranes S2B17H17 (2), n‐S2B16H16 (5) and i‐S2B16H16 (6) were synthesised and also found to exhibit a range of luminescent properties. These macropolyhedral species are very different from the previously unique fluorescent binary borane B18H22 in terms of their structural architectures, by the presence of borane cluster hetero atoms, and, as in the cases of 5 and 6, that their synthetic origins are not derived simply through the modification of B18H22 itself. They consequently greatly expand the possibilities of finding new luminescent inorganic borane species.

Expanding Luminescence Horizons in Macropolyhedral Heteroboranes.

Luminescence is observed in three novel macropolyhedral nineteen- and eighteen-vertex chalcogenaboranes: Se2B17H17 (1), SeB17H19 (3) and SeB18H20 (4). This led us to the recognition that previously published macropolyhedral heteroborane species might also exhibit luminescence. Thus, the known nineteen- and eighteen-vertex dithiaboranes S2B17H17 (2), n-S2B16H16 (5) and i-S2B16H16 (6) were synthesised and also found to exhibit a range of luminescent properties. These macropolyhedral species are very different from the previously unique fluorescent binary borane B18H22 in terms of their structural architectures, by the presence of borane cluster hetero atoms, and, as in the cases of 5 and 6, that their synthetic origins are not derived simply through the modification of B18H22 itself. They consequently greatly expand the possibilities of finding new luminescent inorganic borane species.

Modulating the Microenvironment of Coumarin Dyes within Multihierarchical Supraparticles: En Route toward Versatile Luminescent Dual‐Threshold Temperature Indicators with Ratiometric Readout

AbstractTemperature indicators trace (un)desired thermal impacts across their thermal history upon readout at every point of interest via defined irreversible signal changes. Ratiometric luminescent temperature indicators are attractive due to their fast, sensitive, contactless, spatially‐resolved, and self‐referenced readout. However, they have a limited working range as commonly only one specific temperature‐induced physicochemical effect is exploited. Herein, dual‐threshold temperature indicator supraparticles (SPs) are introduced that expand the working range of individual luminescent probes and enhance the extractable information on the thermal history. These SPs derive their functionality from the synergistic interplay of three spectrally distinguishable luminescent species assembled in one multihierarchical, micrometer‐sized particle of hybrid organic‐inorganic nature. This engineered nanostructure enables the stepwise modulation of the physicochemical microenvironment of two incorporated coumarin species at programmable threshold temperatures, resulting in distinct changes in their emission. As these changes are based on dye‐specific mechanisms that are induced in consecutive temperature regimes, the SPs achieve a scarcely reported broad working range (60–200 °C) with temperature‐dependent response times of minutes to seconds. From a broader perspective, the conceptualized SPs pioneer in how multiple individual luminescent probes with different excitation‐emission properties and indicator mechanisms are synergistically united in one advanced indicator system by precise material engineering.

Mycena lamprocephala, a new luminescent species from the Brazilian Amazon

A luminescent fungus growing on decaying leaves and sticks was collected in terra-firme forest at the upper Cuieiras river, Amazonas, Brazil. Morphological study and phylogenetic analysis (based on ITS+LSU data) confirmed it as a new species of Mycena. Mycena lamprocephala sp. nov. is characterized macroscopically by small, thin, basidiomata with an olivaceous brown pileus and glutinous stipe, and microscopically by diverticulate pleurocystidia, ramose cheilocystidia, and thin, diverticulate and branching pileipellis hyphae. The luminescence of the pileus and of the mycelium in the substrate is typically green and sometimes pulsating. This is the third luminescent species of Mycenaceae described from the Amazon Forest.

Enabling Carbonized Polymer Dots with Color‐tunable Time‐dependent Room Temperature Phosphorescence through Confining Carboxyl Dimer Association

AbstractDeveloping a facile strategy to realize fine‐tuning of phosphorescence color in time‐dependent room temperature phosphorescence (RTP) materials is essential but both theoretically and practically rarely exploited. Through simultaneously confining carboxyl dimer association and isolated carboxyl into the particle via a simple hydrothermal treatment of polyacrylic acid, a dual‐peak emission of red phosphorescence (645 nm) and green phosphorescence (550 nm) was observed from carbonized polymer dots (CPDs). The ratio of the two luminescent species can be well regulated by hydrochloric acid inhibiting the dissociation of carboxyl to promote hydrogen bond. Due to comparable but different lifetimes, color‐tunable time‐dependent RTP with color changing from yellow to green or orange to green were obtained. Based on the crosslinking enhanced emission effect, the phosphorescence visible time was even extended to 7 s through introducing polyethylenimide. This study not only proposes a novel and facile method for developing CPDs with color‐tunable time‐dependent RTP, but also provides a bran‐new non‐conjugated red phosphorescence unit and its definite structure.

Enabling Carbonized Polymer Dots with Color-tunable Time-dependent Room Temperature Phosphorescence through Confining Carboxyl Dimer Association.

Developing a facile strategy to realize fine-tuning of phosphorescence color in time-dependent room temperature phosphorescence (RTP) materials is essential but both theoretically and practically rarely exploited. Through simultaneously confining carboxyl dimer association and isolated carboxyl into the particle via a simple hydrothermal treatment of polyacrylic acid, a dual-peak emission of red phosphorescence (645 nm) and green phosphorescence (550 nm) was observed from carbonized polymer dots (CPDs). The ratio of the two luminescent species can be well regulated by hydrochloric acid inhibiting the dissociation of carboxyl to promote hydrogen bond. Due to comparable but different lifetimes, color-tunable time-dependent RTP with color changing from yellow to green or orange to green were obtained. Based on the crosslinking enhanced emission effect, the phosphorescence visible time was even extended to 7 s through introducing polyethylenimide. This study not only proposes a novel and facile method for developing CPDs with color-tunable time-dependent RTP, but also provides a bran-new non-conjugated red phosphorescence unit and its definite structure.

Single Atom Silver‐Phosphors in Titanosilicate Matrix for Enhanced LED Applications

AbstractSmall metal oligomers have gained significant attention due to their exceptional optoelectronic properties and versatile applications, ranging from sensors to imaging and catalysis. However, the need for matrices (silica, zeolites, or metal‐organic frameworks) to prevent aggregation into larger metallic particles reduces their potential applicability in light‐emitting devices (LEDs) due to their poor electrical properties. To address this issue, a novel semiconductor stabilizer, titanosilicate, is proposed as an innovative solution for Ag‐based luminescent materials. These results show that titanosilicate, characterized by high thermochemical stability and well‐defined semiconducting properties, is an ideal scaffold for Ag‐luminescent species. Optical spectroscopic techniques reveal that Ag‐titanosilicates feature an orange fluorescence with a photoluminescence quantum yield reaching 20%. In contrast, a combination of X‐ray diffraction, TEM, and XEOL‐X‐ray absorption spectroscopic techniques show that, unlike zeolites, the luminescent species consist of single Ag atoms. The electroluminescent properties of the proposed Ag‐titanosilicate are further investigated within a conventional LED architecture by using the new material as an emissive layer. The developed proof‐of‐concept LED exhibits a significant improvement of the ZEOLEDs, where a smaller low turn‐on voltage of 2 V (enabling energy‐efficient operation) and high color rendering index of 80 introduces exciting prospects for developing advanced Ag‐LED phosphors.

Coreactant-free dual-emitting conjugated polymer for ratiometric electrochemiluminescence detection of SARS-CoV-2 RdRp gene

Constructing mono-luminophor-based electrochemiluminescence (ECL) ratio system is a great challenge due to the limitations of the luminescent species with dual-signal-output, luminescence efficiency and coreactant. This work developed carboxyl-functionalized poly[9,9-bis(3'-(N,N-dimethylamino) propyl)-2,7-fluorene]-alt-2,7-(9,9 dioctylfluorene)] nanoparticles(PFN NPs) as dual-emitting luminophors, which can synchronously output strong cathodic and anodic ECL signals without any exogenous coreactants. The inherent molecular structure enabled efficient intramolecular electron transfer between tertiary amine groups and backbone of PFN to generate strong cathodic and anodic ECL emission. Particularly, H+ in aqueous solution played an irreplaceable role for cathodic ECL emission. The silver nanoparticles (AgNPs) were developed as signal regulator because of their excellent hydrogen evolution reaction (HER) activity, which significantly quenched the cathodic signal while kept the anodic signal unchanged. The dual-emitting PFN NPs cleverly integrated signal regulator AgNPs and bicyclic strand displacement amplification (SDA) to construct a coreactant-free mono-luminophor-based ratiometric ECL sensing for SARS-CoV-2 RdRp gene assay. The strong dual-emitting of PFN NPs and excellent quenching effect of AgNPs on cathodic emission endowed the biosensor with a high detection sensitivity, and the detection limit was as low as 39 aM for RdRp gene. The unique dual-emitting properties of PFN NPs open up a new path to construct coreactant-free mono-luminophor-based ECL ratio platform, and excellent HER activity of AgNPs offers some new thoughts for realizing ECL signal changes.

Exploring Ln(III)-Ion-Based Luminescent Species as Down-Shifters for Photovoltaic Solar Cells.

In this work, we have compiled our research on lanthanide-based luminescent materials for use as down-shifter layers in photovoltaic (PV) mini-modules. The complexes we have prepared (C1-17), with formulas [Eu2(phen)2(bz)6] (C1), [Eu2(bphen)2(bz)6] (C2), [Eu(tta)3bphen] (C3), [Eu(bta)3pyz-phen] (C4), [Eu(tta)3pyz-phen] (C5), [Eu(bta)3me-phen] (C6), [Er(bta)3me-phen] (C7), [Yb(bta)3me-phen] (C8), [Gd(bta)3me-phen] (C9), [Yb(bta)3pyz-phen] (C10), [Er(tta)3pyz-phen] (C11), [Eu2(bz)4(tta)2(phen)2] (C12), [Gd2(bz)4(tta)2(phen)2] (C13), [EuTb(bz)4(tta)2(phen)2] (C14), [EuGd(bz)4(tta)2(phen)2] (C15), [Eu1.2Gd0.8(bz)4(tta)2(phen)2] (C16), and [Eu1.6Gd0.4(bz)4(tta)2(phen)2] (C17), can be grouped into three families based on their composition: Complexes C1-6 were synthesized using Eu3+ ions and phenanthroline derivatives as the neutral ligands and fluorinated β-diketonates as the anionic ligands. Complexes C7-11 were prepared with ligands similar to those of complexes C1-6 but were synthesized with Er3+, Yb3+, or Gd3+ ions. Complexes C12-17 have the general formula [M1M2(bz)4(tta)2(phen)2], where M1 and M2 can be Eu3+, Gd3+, or Tb3+ ions, and the ligands were benzoate (bz-), 2-thenoyltrifluoroacetone (tta-), and 1,10-phenanthroline (phen). Most of the complexes were characterized using X-ray techniques, and their photoluminescent properties were studied. We then assessed the impact of complexes in the C1-6 and C12-17 series on the EQE of PV mini-modules and examined the durability of one of the complexes (C6) in a climate chamber when embedded in PMMA and EVA films. This study emphasizes the methodology employed and the key findings, including enhanced mini-module efficiency. Additionally, we present promising results on the application of complex C6 in a bifacial solar cell.

Cubane Copper(I) Iodide Clusters with Remotely Functionalized Phosphine Ligands: Synthesis, Structural Characterization and Optical Properties

We present here the synthesis, chemical, and photophysical study of a series of three new copper halide derivatives, namely 2a–c. They are all tetranuclear copper-iodide clusters of general formula [Cu(μ3-I)P]4 consisting of a cubane-like {Cu4I4} motif and P = phosphine. They differ in the type of the phosphines used as ligands: a monophosphine with a single pendant ester unit (complex 2a), two pendant ester units (2b), and a diphosphine containing two esters in the linker (2c). The molecular structure of the complexes was determined by single-crystal X-ray diffraction analysis. All the investigated derivatives were found to be photo- and thermally-stable luminescent species. In the solid state, the complexes display intense and long-lived photoluminescence in the orange region with PLQY values of 0.43–0.84 at room temperature associated mainly with a 3CC excited state with mixed 3XMCT character.

Initiation and recovery of damage initiated by UV irradiation in luminescent solar concentrators deposited in ambient conditions

Photopolymerization of thin, dye-doped acrylate-based layers under ambient conditions often requires high concentrations of photoinitiators. The radical storm created during polymerization has been shown to cause damage to the embedded fluorescent dyes; some of this damage is repaired upon exposure to air, but a fraction of the damaged molecules do not repair. This work presents a more detailed optical study of the environmental effects, nature of the initiator, and resulting fluorescence of the dye molecules caused by photopolymerization, all factors necessary to understand and control to allow ambient inkjet printing of these luminescent species.

Photophysical Properties of Pyrene‐Substituted nido‐Carborate Anion and the Change of Luminescence Species by Counter Cations in Solution and Solid States

AbstractThis study reports unique luminescent properties of pyrene‐substituted nido‐carborate anion (PYnCA) with two counter cations, tetrabutylammonium (NBu4+) and tetraphenylphosphonium (PPh4+). It is revealed that PYnCA shows twisted intramolecular charge transfer (TICT) emission by the change of the dihedral angle between pyrene and the CcageCcage bond in the carborane unit in the excited state. Although the structure of nCA is almost same as that of ortho‐carborane (oC), the photophysical processes of both pyrene‐substituted compounds are completely different. The study also succeeds in modulating the luminescence species by counter cations in both solution and solid states. To the best of the current knowledge, this is the first report that anion‐based luminescent materials can show the different luminescent species not only in solution but also in the mechanochromic behaviors depending on the type of counter cations. This fundamental research on nCA demonstrates anion‐based emitters as a new platform for stimuli‐responsive materials.

An Intelligent Laser-Free Photodynamic Therapy Based on Endogenous miRNA-Amplified CRET Nanoplatform.

Laser-free photodynamic therapy (PDT) is a promising noninvasive therapeutic modality for deep-seated tumor, yet is constrained by low efficiency due to the limited stimulation strategies. Herein, a novel miRNA-responsive laser-free PDT was developed through metal-organic frameworks (MOFs)-mediated chemiluminescence resonance energy transfer (CRET) nanoplatform. The photosensitizer chlorin e6 (Ce6)-loaded MOFs were functionalized with hairpin nucleic acids for sensitive responsiveness of tumor biomarker miRNA through catalytic hairpin assembly (CHA), which enabled the amplified assembly of horseradish peroxidase (HRP)-mimicking hemin/G-quadruplex DNAzyme on MOFs. Simultaneously, the on-MOF assembled DNAzymes efficiently catalyzed chemiluminescence reaction to stimulate adjacent Ce6 in the presence of luminol and H2 O2 , thus allowing the CRET-mediated Ce6 luminescence and reactive oxygen species (ROS) generation for self-illuminating PDT. The CRET nanoplatform achieved significant malignant cell apoptosis and tumor inhibition effects without external laser irradiation. It is envisioned that the miRNA-amplified CRET nanoplatform might be a selective and highly efficient antitumor nanomedicine for precise theranostic.