Emission Phenomena Research Articles

Tetracoordinate Boron(III) Compound with BF2O2 Skeleton as Monomer for the Synthesis of Tetracoordinate Oligoboranes

A new neutral tetracoordinate boron(III) compound 1 containing a BF2O2 skeleton was used as a monomer to produce a mixture of oligoboranes featuring sp3 B–B bonds via the Wurtz-type coupling reaction with metallic sodium in boiling toluene. 1, which is a difluoroboron compound that contains an O,O-donor ligand, showed intense greenish light emission in crystalline form with fluorescence quantum yield (ΦF) of 0.56 and aggregation-induced emission (AIE) phenomenon with ΦF of 0.25. The molecular structure of 1 was characterized by single-crystal X-ray diffraction and confirmed by 1H, 11B, 13C, 19F NMR and elemental analysis, while the mixture of oligomers was characterized by solution 1H, 11B, 13C, and 19F NMR and in the solid-state by 11B MAS NMR analysis. The Matrix-Assisted Laser Desorption/Ionization-Time-Of-Flight (MALDI-TOF) analysis confirmed that the oligoboranes are composed of a mixture of diborane and triborane species. Both in the solution and the solid state, 11B NMR analysis confirmed the boron atoms maintain the tetracoordination with sp3 hybridization. The Density Functional Theory (DFT) analysis was used to get more insights into the molecular structure of the diborane and triborane species.

Highly efficient tunable mid-infrared luminescence achieved by crystal field modulation of CsPb1-xHoxBr3 halide perovskite AlF3-based fluoride glass

Mid-infrared (MIR) light sources have gained significant importance across various applications in spectroscopy, sensing, astronomy, communications and medical surgery. The diverse spectral characteristics of rare earth ions, particularly lanthanide ions, stemming from their distinctive 4f intershell transitions, offer a multitude of potential transitions spanning the UV-visible-infrared spectrum. Despite recent advancements in MIR gain luminescence, the investigation of tunable MIR luminescence mechanisms remains a major technical challenge. Herein, an effective mechanism to modulate the local crystal field of rare earth ions by altering its crystal structure has been revealed, resulting in tunable broad-spectrum emission in the MIR luminescence range of 2800-3000 nm and multi-peak emission in the near-infrared band of Ho3+. Notably, the local crystal field of Ho3+ is adjusted by manipulating the lattice symmetry of CsPb1-xHoxBr3 perovskite through the incorporation of fluoride glass reticulation to control the crystal size of the perovskite and thereby modify the lattice symmetry of CsPb1-xHoxBr3 perovskite. The energy level transition of Ho3+ is influenced by adjusting the crystal field asymmetry, resulting in the splitting of the 5I6 energy level depending on the crystal field. This cleavage affects the transitions from the 5I5 level to 5I6 at 1480 nm and from 5I6 to 5I7 at 2880 nm. As 5I6 acts as the common upper level for the two emission peaks, the infrared peaks at 1480 nm and 2880 nm widen and develop into a dual-peak emission phenomenon. The infrared luminescence produced aligns closely with the distinctive infrared absorption peaks of carbon dioxide, leading to the development of a convenient, high-precision device for monitoring of CO2 concentration in hydrogen energy in real time. These findings are anticipated to pave the way for extensive utilization of novel tunable MIR luminescence.

Comprehensive review of protein imaging with AIEgens conjugated probes: From concentration to conformation

Proteins are an essential component of living organisms, and the study of their structure and function is of great importance in biological and medical research. In recent years, the remarkable phenomenon of aggregation-induced emission (AIE) has been extensively utilized in protein detection. Significant progress has been made in the development of aggregation-induced emission luminogens (AIEgens), which have proven invaluable in protein imaging. This review highlights AIEgen-conjugated probes for imaging proteins in tumor cells through various mechanisms, including physical interactions, ligand binding, and enzymatic cleavage. These probes exploit the AIE effect to enhance the signal-to-noise ratio, providing important tools for protein research. Additionally, these probes can be used to study structural changes in intracellular protein phase separation processes, such as unfolded, misfolded, fibrous, and amorphous aggregates. The above research achievements presented lay the foundation for the widespread application of AIEgen-conjugated probes in the biomedical field and are expected to stimulate further development in related research.

Reversible addition-fragmentation chain transfer enhanced aggregation signal-on fluorescence detection of alkaline phosphatase.

The instability of the signal intensity of fluorescent biosensors and the false signals have been significant factors affecting the performance of biosensors. Herein, a novel signaling system is devised through the application of reversible addition-fragmentation chain transfer (RAFT) polymerization with monomers containing the tetraphenylethylene (TPE) groups. TPE exhibits an aggregation-induced emission (AIE) phenomenon in certain solvents, mainly due to the blockage of the rotation of its four benzene rings, which also exist in the aggregated state. With this property, a series of molecules are modified based on click chemistry for RAFT polymerization using Fe3O4 magnetic beads as the carriers, and stable aggregated luminescent TPE polymers are formed on the surface of magnetic beads to realize the transformation of fluorescence signal from "0" to "1". In addition, the fluorescence signal demonstrates a positive correlation with alkaline phosphatase (ALP) activity, which can be quantified by measuring the fluorescence intensity. The biosensor exhibits high sensitivity and good linearity in the range of 0.1-5 U/L, with a LOD of 0.079 U/L. Furthermore, the designed strategy demonstrated satisfactory performance in the quantitative determination of ALP activity in serum samples, indicating that the signaling system developed by combining RAFT polymerization and AIE molecules has an important application in the field of fluorescent biosensors.

On-chip warped three-dimensional InGaN/GaN quantum well diode with transceiver coexistence characters

Featured with light emission and detection coexistence phenomenon, nitride-based multiple-quantum-well (MQW) diodes integrated chip has been proven to be an attractive structure for application prospects in various fields such as lighting, sensing, optical communication, and other fields. However, most of the recent reports are based on planar structures. Three-dimensional (3D) structures offer extra advantages in direction and polarization and absorption modulation and may start a new way to make the same thing over and over with interesting properties. In this paper, we designed and fabricated a single-cantilever InGaN/GaN MQW diode with warped 3D microstructure via standard microfabrication technology. Experimental results indicate that the strain architecture of the multi-layer materials is the key principle for the self-warped device. The planar structure will bear greater compressive stress while the warped beam part has less stress, resulting in differences in the optical and electrical performance. The strain-induced band bending highly influences the emission and detection properties, while the warped structure will introduce direction selectivity to the 3D device. As an emitter, 3D structures have a directional emission with lower turn-on voltage, higher capacitance, increased luminous intensity, higher external quantum efficiency (EQE), high -3dB bandwidth, and redshifted peak wavelength. Besides, it can serve as an emitter for directional-related optical communication. As a receiver, 3D structures have lower dark-current, higher photocurrent, and red-shifted response spectrum and also show directional dependence. These findings not only deepen the understanding of the working principle of the single-cantilever GaN devices but also provide important references for device performance optimization and new applications in visible light communication (VLC) technology.

Monitoring of insulator pollution discharge in overhead distribution network based on acoustic emission technology

Abstract During the continuous operation of the distribution network, dirt often accumulates on the surface of insulators. Once encountering a humid climate environment, it may cause accidental discharge, leading to the occurrence of flashover pollution accidents. In order to effectively monitor this issue, this study adopted a monitoring method based on acoustic emission technology. This article introduces the discharge process and acoustic emission phenomenon of insulators in overhead distribution networks under pollution conditions. By using emission signal detection devices, acoustic signals generated during insulator discharge are captured. And the wavelet denoising algorithm was used to process its signal, based on which the discharge characteristics of insulator pollution in the overhead distribution network were extracted. The emission amount of insulator pollution in the overhead distribution network was determined according to the set threshold, achieving monitoring of pollution emissions. The results indicate that the proposed method can accurately monitor the discharge of insulators in overhead distribution networks, provide scientific basis for timely maintenance measures, and improve the operational safety and reliability of distribution networks.

Operation of Si field emitter arrays in an N2 environment

Field Emitter Arrays (FEAs) have the potential to operate at high power, high frequencies, and endure harsh environments. However, vacuum packaging these devices poses a challenge due to the sensitivity of the emission phenomena to the surface properties of the cathode, such as the work function and the tip radius. Studying the effect of different residual gases on FEAs can enhance our understanding of the interaction between the emission surface and the environment and help estimate the permissible amount of residual gases within the package. In this study, the effect of N2 exposure on 500×500 Silicon Field Emitter Arrays (Si-FEAs) was investigated. The device was exposed to 10 000 Langmuir (L) of N2 at 10-7 Torr. During the exposure, the anode current increased from 4.7 μA to 16 μA. However, this enhancement in current was temporary, and upon closing the leak valve, the anode current gradually returned to the pre-exposure level. No significant change in current was observed when the device was powered off during N2 exposure. The extent of current enhancement showed a direct relationship with the partial pressure of N2. These results suggest that the presence of N2 in a vacuum package does not degrade the performance of Si-FEAs.

Understanding the Role of NHC Ditopic Ligand Substituents in the Molecular Diversity and Emissive Properties of Silver Complexes.

Silver bis(carbene) complexes featuring ditopic N-heterocyclic carbene (NHC) ligands have been synthesized which enable the assembly of supramolecular architectures via reaction with silver triflate. Through a systematic exploration of crystal structures and emissive properties, this study investigates the impact of the substituents on the NHC ditopic ligands [R-Im-2-Z-py], where R = Me, benzyl (Bz), or 2-naphthylmethyl (NaphCH2), and Z = H or Cl in the structural framework and emissive properties observed in the silver bis(carbene) or polynuclear species. Remarkably diverse structural motifs emerge in both of them, predominantly influenced by the choice of R wingtip and second by the Z substituent. Also the emissive quantum yield of the complexes is mostly governed by the selection of the R wingtip and further modulated by the Z substituent. Several of the mono and polynuclear complexes exhibit complex emissive profiles, including the observation of dual emission phenomena. Particularly noteworthy is the complex [Ag(NHC)]2]OTf (R = Bz, Z = Cl), which demonstrates an exceptionally intense single blue emission with a remarkable solid-state quantum yield (Φ) of 24%.

Exploration of the Photoluminescence Behavior and Emission Mechanism of Thioester Polyacrylamide Tablets During the Gradual Increase of Molecular Weight.

To enhance the photoluminescence (PL) of unconventional luminescent compounds, particularly their persistent room temperature phosphorescence (p-RTP) performance, compressing the powder into tablets has been demonstrated as a viable approach. Nevertheless, the alterations in the emission capability of PL in compacted tablets have not been comprehensively investigated. In this study, four polyacrylamide (PAM) with controllable molecular weight (MW) are fabricated from powder to tablets, and their PL emission properties are thoroughly examined and compared with corresponding powders to elucidate the emission mechanism. As MW increases, both PL and p-RTP emissions of the tablets gradually intensify, exhibiting significant enhancement compared to the corresponding powder while retaining the characteristic blue shift. Through small angle X-ray scattering (SAXS), construction of molecular models for tablets, detailed analysis of molecular interactions, and theoretical calculations are conducted to reasonably explain these emission phenomena using clustering-triggered emission (CTE) and average packing density promoted emission (PDE) mechanisms. These findings not only advance the understanding of nonconventional luminogens' emission mechanisms but also offer new insights for preparing nonconventional luminescent polymers with controllable p-RTP emission performance.

Carbon Dot-Based Composite with Color Excitation-Dependent Room-Temperature Phosphorescence for Advanced Optical Encryption and Anticounterfeiting.

The phenomenon of multicolor afterglow emission has attracted considerable attention in information encryption, bioimaging, and sensing. Consequently, there is a growing demand for the development of multicolor afterglow and phosphorescence switching methods utilizing carbon dot (CD) materials. Herein, multicolor room-temperature phosphorescence (RTP) emission in CD-based materials (PM-CD@BA composite) was achieved by developing multiple emission centers and tuning the excitation wavelength. The color of the afterglow observed in this composite covered from the deep-blue to the green region. The experimental results reveal that under heating treatment, the CDs embedded in inorganic boric acid/B2O3 matrix materials and a rigid framework generated in the composite system effectively suppressed the nonradiative transition and promoted the RTP emission. Finally, high-resolution multilevel RTP 2D code data encryption was realized by inkjet printing technology. The developed concepts of information encryption and anticounterfeiting exhibit the significant potential of CD-based afterglow materials applied in advanced optical applications.

A Carbazole-based Fluorescent Probe with AIE Performance and a Large Stokes Shift for Peroxynitrite Detection and Imaging in Live Cells.

A carbazole-based fluorescent probe YCN with AIE performance and a large Stokes shift (242nm) shift was synthesized by attaching 4-acetonitrile pyridine to the 3-phenylaldehyde butylcarbazole. Its structure was characterized by 1H NMR, 13C NMR and MS. Probe YCN has high selectivity and sensitivity toward ONOO-. The addition of ONOO- to the probe YCN solution results in a noticeable color change from pale yellow to colorless under natural light, and a fluorescent color change from bright orange-yellow to bright yellow-green under a 365nm UV lamp, which can be distinguished by the naked eye. The research results on the reaction mechanism showed that when YCN reacted with ONOO-, -C = C- was oxidized and broken into -CHO, and the ICT effect was significantly inhibited, resulting in changes in UV absorption and fluorescence emission phenomenon. The recognition mechanism was verified by 1H NMR, mass spectrometry (MS) and density function theory (DFT) calculations. The experiments of live cells imaging suggested that compound YCN can be used as a fluorescent probe for the detection of ONOO- in HeLa cells. This result indicates that YCN has potential application prospects in the biological aspects.

A data-driven model for the field emission from broad-area electrodes

Electron emission from cathodes in high field gradients is a quantum tunneling effect. The 1928 Fowler–Nordheim field emission (FE) equation and the 1956 Murphy–Good FE equation have traditionally been key in describing cold field emissions, offering estimates for emitters for almost a century. Nevertheless, applying FE theory in practice is often constrained by the lack of data on the distribution and geometry of the emission sites. Predictions become more challenging with an uneven electric field distribution at the cathode surface. Consequently, FE formulations are frequently calibrated using current–voltage data after test, limiting their efficacy as true predictive models.This study develops an alternative model for field emission using a data-driven predictive approach based on (1) vast experimental data, (2) electrostatic simulations of the cathode surface, and (3) detailed material and geometry properties, which together overcome these limitations. The objective of this work is to develop and harness this comprehensive dataset to train a machine learning model capable of providing precise predictions of the cathode current in order to further the understanding and application of field emission phenomena. More than 259 h of experimental data have been processed to train and benchmark some of the well-known machine learning models. After two stages of optimization, a coefficient of determination >98% is achieved in the prediction total field emission current using ensemble models.

Crystal structure and spectral tuning of Eu2+/Eu3+ co-activated Na2Ba1-xSrxCa(PO4)2 phosphors with high thermal stability

The coupling of UV LED chips with phosphors to produce white or color-tunable light is still a challenge. In this work, we propose a simple rare earth occupation site engineering method to adjust the valence of doped Eu ions. Based on the Ba2+ substituted by Sr2+, new Eu2+/Eu3+ co-activated Na2Ba1-xSrxCa(PO4)2 (NB1-xSxCP) phosphors were designed and successfully synthesized. In NB1-xSxCP, the Ba2+/Sr2+ site is occupied by Eu2+, while the Ca2+ site is occupied by Eu3+. The coupled broad blue 448 nm and sharp red 619 nm luminescence under 321 nm excitation has demonstrated the coexistence of Eu2+ and Eu3+. This double emission phenomenon is studied in terms of the fluorescence lifetime as well as lattice distortion induced by the substitution ions. With the increased substitution of Sr, the luminescence of NB1-xSxCP:0.03Eu2+/3+ can be tuned from blue to red crossing the warm-white region. When x = 0.3, the chromaticity coordinates is located at (0.3779, 0.2495). The integrated intensity of Na2Ba0.7Sr0.3Ca(PO4)2:0.03Eu2+/3+ at 150℃ remains 90.9 % of that at room temperature, while the chromaticity shift (ΔE) can be calculated as 15 ×10−3. The Eu2+/Eu3+ co-activated NB1-xSxCP is a potential candidate for single-phase color-tunable phosphors used for light-tunable applications due to the combining contributions from both Eu3+ and Eu2+ ions.

Secondary Ion Emissions of Tm and Tb Targets Under Bombardment With Cluster Ions

ABSTRACTIn this work, the features of secondary emission phenomena were investigated under cluster bombardment. The emission of ion‐photons, secondary ions, and electrons associated with the thermal peak regime were experimentally carried out. The experiments were conducted using modernized a static magnetic mass spectrometer. The integral yield of secondary ion and electron emission was measured by bombarding Tb and Tm targets with cluster ions Aum− (m = 1–9) and Bim− (m = 1–7) within the energy range of 1–21 keV for the bombarding ions. Additionally, the integral yield of ion‐photon emission was measured by bombarding a Tm target with cluster ions Bim− (m = 1–5) within the same energy range. The experimental results showed that an increase in the yield of ion‐photon emission, secondary ion, and ion‐electron emission was observed with an increase in the number of atoms bombarded by cluster ions. This can be explained the formation of thermal peaks under dense collision cascades.

Exploring the DNA-binding and anticancer potential of polypyridyl ruthenium(II) complexes

Organometallic medicines based on ruthenium (Ru) have attracted interest as chemotherapeutic and bioimaging agents due to their low toxicity and superior physical optical characteristics. However, there are still no ideal candidates in clinical trials due to the lack of understanding of the structure-activity relationships (SARs) of polypyrodyl Ru(II) complexes. Though increasing the electron-donating ability of the ligands has been proven to benefit bioactivity due to the fast hydroxylation rate between chlorine and DNA, the total electronic effects are much more important, especially for the binding modes between Ru(II)-polypyridyl complexes and DNA. By evaluating the electron-donating ability of the ligand complexes 1 - 4 through density functional theory (DFT) calculations, bioactivities tests, and docking studies, we investigated the relationship between the structures of Ru(II) complexes and cytotoxicity. Our findings showed that it was insufficient to merely consider the impact of electron-donating effects on biological activities in place of interaction modes. Furthermore, the cellular imaging study investigated the complex with phenyl substituents (1) and confirmed that the main target was DNA. Besides, the “off-on” emission phenomena of complex 1 indicated that there is also covalent interaction with DNA. These findings offer valuable insight into the development of SARs of polypyrodyl Ru(II) complexes.

Multi-component synthesis and enhanced photophysical study of novel azolo[1,5-a]pyrimidine based dyes

A series of novel fluorophores were obtained based on azolo[1,5-a]pyrimidines (APs) through multicomponent and oxidation reactions, starting from aminoazoles, morpholineacrylonitrile, and 4-(dimethylamino)benzaldehyde. Photophysical studies, as well as DFT calculations have been performed for the obtained APs. Aggregation-induced emission (AIE) phenomenon was demonstrated for fluorophores containing an aromatic substituent at the C-2 position of the azolo[1,5-a]pyrimidine core. It was observed that fluorophore 6d exhibited reversible mechanochromic luminescence. Two-photon absorption cross-section was measured for all obtained APs. In addition, cell staining resulted in identical intracellular distribution under excitation at 405 nm, 488 nm and 561 nm.

Discovery of a novel marine bacterial AIEgen that lights up specific G-quadruplexes

The emergence of aggregation-induced emission (AIE) phenomenon two decades ago marked a significant advancement in chemical science. It has fostered the development of versatile AIE luminogens (AIEgens) applicable in bioimaging, optoelectronics, and biochemical sensing. However, the application potential of synthetic AIEgens is limited owing to their constrained chemical space, environmental concerns, and uncertain biocompatibility. Consequently, the pursuit of naturally derived AIEgens (BioAIEgens) is considered a promising solution to developing next-generation AIEgens. Here, we report the discovery of 2-(2-hydroxy-6-methoxy-3-propionylphenyl)quinazolin-4(3H)-one (HMPQ) from marine bacterial metabolite as AIEgen for the first time. HMPQ shows its unique fluorescence mechanism through excited-state intramolecular proton transfer. Comprehensive photophysical assessments unveiled that HMPQ varied emissions in diverse solvents and solid-state polymorphic forms. Notably, HMPQ exhibited specific binding affinity to G-quadruplexes (G4s), illuminating these non-canonical nucleic acid structures without altering their conformation. Its remarkable safety profile and precise cellular visualization of G4 structures imply HMPQ’s potential in biological applications, opening new avenues for utilizing BioAIEgens as G4 probes.

Ethanol and Gd3+ activated aggregation induced delayed fluorescence in copper nanoclusters for detection of Cr(VI)

In recent years, significant emphasis has been dedicated towards investigating aggregation-induced emission (AIE) phenomena, and a notable addition to this emerging field is aggregation-induced delayed fluorescence (AIDF). Here, we proposed two different strategies to produce AIDF-based luminescent materials at room temperature from glutathione-capped CuNCs (GSH-CuNCs) by (1) simply modifying the solvent environment and (2) introducing gadolinium (Gd3+) ions. The synthesized GSH-CuNCs displayed weak fluorescence (Fl) emission in aqueous solution with a short delayed lifetime of 3.2 μs and quantum yield (QY) of only 1.42 %. However, introducing GSH-CuNCs to an ethanol medium promptly led to enhanced delayed Fl emission with a significantly delayed lifetime of 21.8 μs and a high QY of 89.2 %. Moreover, introducing Gd3+ ions to the aqueous GSH-CuNC solution also enhances delayed Fl emission with a delayed lifetime of 13.6 μs and a high QY of 79.5 %. Analysis of transmission electron microscopy and dynamic light scattering data showed that both the ethanol medium and Gd3+ addition endows controlled aggregation of GSH-CuNCs, enabling successful harvesting of triplet states and ultimately leading to the AIDF phenomenon. Moreover, the AIDF harnessed from GSH-CuNCs by Gd3+ was successfully employed to detect Cr6+ ions in an aqueous solution with excellent selectivity.

Red/near-infrared (NIR) difluoroboron β-diketonate derivatives with reversible mechanochromism for cellular imaging

Near-infrared (NIR) fluorophores have promoted the development of materials for bioimaging, but traditional NIR dyes usually suffer from aggregation-caused quenching (ACQ), impeding their applications. Herein, we propose two difluoroboron β-diketonate complexes TBO and TBS, consisting a donor–acceptor (D-A) structure with triphenylamine (TPA) moiety as an electron donors and difluoroboron as well as furan or thiophene building block as an electron acceptor. The theoretical calculation and optical data shows that both of them have intramolecular charge transfer (ICT) characteristics. Such ICT characteristics endow them with both solvatochromism and dual-state emission (DSE) properties. In the solvent CH2Cl2, the emission wavelength of TBO ranges from 550 nm to 750 nm, with a low fluorescence quantum yield (Φ = 7.0 %). However, in the less polar solvent hexane, the emission wavelength blue-shifts, with an increased Φ reaching up to 18 %. Moreover, TBO and TBS exhibit mechanochromic characteristics and rare multi-channel fluorescence emission phenomena at solid-state. Their solid-state samples can emit fluorescence in four spectral bands with maximum emission wavelengths at 300 nm, 400 nm, 600 nm, and 770 nm under excitation at 240 nm. These unique optical properties are expected to be utilized for detecting polarity of system and deformation. Moreover, according to the results of cell imaging and flow cytometry, TBO molecular were easily internalized into Hela cells and distributed in the cytoplasm with strong red fluorescence. Therefore, this research inspires more insight into development of NIR luminogens for biomedical imaging.

Signatures of fatigue crack growth from acoustic emission repeaters

Since the discovery of fatigue phenomena, scientific research has constantly sought to understand and anticipate the failure of materials due to fatigue to mitigate unforeseen accidents and malfunctions in various technical fields. Numerous studies using acoustic emission (AE) – a key method in non-destructive testing – have shown a correlation between acoustic activity and fatigue damage. However, these measurements suffer from the non-specific nature of AE signals, which may be due to various physical sources. To investigate further the mechanisms of AE emission associated with fatigue, we study the groups of acoustic signals generated by fatigue cracking in metals. These so-called acoustic multiplets are characterized by highly correlated waveforms, are repeatedly triggered over many successive loading cycles at nearby stress levels and originate from a single location. These acoustic signatures produced during the propagation of fatigue cracks in alloys are automatically detected by a dedicated algorithm, grouped into multiplets and analyzed to understand the physical mechanisms from which they originate. By synchronizing their detection with digital image correlation measurements of fracture mechanics quantities, the investigation of this acoustic emission phenomenon shows that two mechanisms are at the origin of the multiplets: repeated local friction over fracture surfaces, and incremental crack propagation in the Paris regime, probably due to the reactivation of crack tip plasticity at each cycle. These two multiplet types serve as acoustic signatures, distinctly indicating the existence and propagation of a fatigue crack.