Recent Advances in Electroluminescent Metallic Nanoclusters: From Materials to Devices.

Metallic nanoclusters (MNCs) were developed rapidly in recent decades, owing to their unique electronic structures and excited state characteristics, leading to their wide applications. Luminescence as one of the most important functions for MNCs has also been used to realize biodetection, displays, and lighting, through either electrochemiluminescence (ECL) or electroluminescence (EL). Both emissive properties and electrochemical activities of MNCs were utilized to enhance ECL and EL through facilitating exciton formation and radiation, rendering the rapid emerging of the latter in the last ten years. Through ligand modification, radiative excited-state components were increased to realize state-of-the-art photo- and electroluminescence efficiencies up to ∼100% and ∼30%, as well as ultralow biodetection limits. Nonetheless, material selection space and processing technologies are still limited. Herein, we overview and discuss recent advances of MNCs-based ECL and EL, through both aspects of materials/systems and devices, which would enlighten continuous innovations in optoelectronic MNCs.

Pre-Adsorbed H-Mediated Electrochemiluminescence.

In conventional electrochemiluminescence (ECL) systems, the presence of the competitive cathodic hydrogen evolution reaction (HER) in aqueous electrolytes is typically considered to be a side reaction, leading to a reduced ECL efficiency and stability due to H2 generation and aggregation at the electrode surface. However, the significant role of adsorbed hydrogen (H*) as a key intermediate, formed during the Volmer reaction in the HER process, has been largely overlooked. In this study, employing the luminol-H2O2 system as a model, we for the first time demonstrate a novel H*-mediated coreactant activation mechanism, which remarkably enhances the ECL intensity. H* facilitates cleavage of the O-O bond in H2O2, selectively generating highly reactive hydroxyl radicals for efficient ECL reactions. Experimental investigations and theoretical calculations demonstrate that this H*-mediated mechanism achieves superior coreactant activation compared to the conventional direct electron transfer pathway, which unveils a new pathway for coreactant activation in the ECL systems.

Unveiling the Dynamic Electrocatalytic Activity of Online Synthesized Bimetallic Nanocatalysts via Electrochemiluminescence Microscopy.

Effective bimetallic nanoelectrocatalysis demands precise control of composition, structure, and understanding catalytic mechanisms. To address these challenges, we employ a two-in-one approach, integrating online synthesis with real-time imaging of bimetallic Au@Metal core-shell nanoparticles (Au@M NPs) via electrochemiluminescence microscopy (ECLM). Within 120 s, online electrodeposition and in situ catalytic activity screening alternate. ECLM captures transient faradaic processes during potential switches, visualizes electrochemical processes in real-time, and tracks catalytic activity dynamics at the single-particle level. Analysis using ECL photon flux density eliminates size effects and yields quantitative electrocatalytic activity results. Notably, a nonlinear activity trend corresponding to the shell metal to Au surface atomic ratio is discerned, quantifying the optimal surface component ratio of Au@M NPs. This approach offers a comprehensive understanding of catalytic behavior during the deposition process with high spatiotemporal resolution, which is crucial for tailoring efficient bimetallic nanocatalysts for diverse applications.

One-Dimensional Covalent Organic Framework with Improved Charge Transfer for Enhanced Electrochemiluminescence.

We present a dimensional regulating charge transfer strategy to achieve an enhanced electrochemiluminescence (ECL) by constructing a one-dimensional pyrene-based covalent organic framework (1D-COF). The dual-chain-like edge architecture in 1D-COF facilitates the stabilization of aromatic backbones, the enhancement of electronic conjugations, and the decrease of energy loss. The 1D-COF generates enhanced anodic (92.5-fold) and cathodic (3.2-fold) signals with tripropylamine (TPrA) and K2S2O8 as the anodic and cathodic coreactants, respectively, compared with 2D-COF. The anodic and cathodic ECL efficiencies of 1D-COF are 2.08- and 3.08-fold higher than those of 2D-COF, respectively. According to density functional theory (DFT), the rotational barrier energy (ΔE) of 1D-COF enhances sharply with the increase of dihedral angle, suggesting that the architecture in 1D-COF restrains the intramolecular spin of aromatic chains, which facilitates the decrease of nonradiative transitions and the enhancement of ECL. Furthermore, 1D-COF can be used to construct an ECL biosensor for sensitive detection of dopamine.

Off-Grid Electrogenerated Chemiluminescence with Customized p-i-n Photodiodes.

Electrochemiluminescence (ECL) is the generation of light induced by an electrochemical reaction, driven by electricity. Here, an all-optical ECL (AO-ECL) system is developped, which triggers ECL by the illumination of electrically autonomous "integrated" photoelectrochemical devices immersed in the electrolyte. Because these systems are made using small and cheap devices, they can be easily prepared and readily used by any laboratories. They are based on commercially available p-i-n Si photodiodes (≈1 € unit-1), coupled with well-established ECL-active and catalytic materials, directly coated onto the component leads by simple and fast wet processes. Here, a Pt coating (known for its high activity for reduction reactions) and carbon paint (known for its optimal ECL emission properties) are deposited at cathode and anode leads, respectively. In addition to its optimized light absorption properties, using the commercial p-i-n Si photodiode eliminates the need for a complicated manufacturing process. It is shown that the device can emit AO-ECL by illumination with polychromatic (simulated sunlight) or monochromatic (near IR) light sources to produce visible photons (425 nm) that can be easily observed by the naked eye or recorded with a smartphone camera. These low-cost off-grid AO-ECL devices open broad opportunities for remote photodetection and portable bioanalytical tools.

Extending the Operational Lifetime of Electrochemiluminescence Devices by Installing a Floating Bipolar Electrode.

Electrochemiluminescence (ECL) holds significant promise for the development of cost-effective light-emitting devices because of its simple structure. However, conventional ECL devices (ECLDs) have a major limitation of short operational lifetimes, rendering them impractical for real-world applications. Typically, the luminescence of these devices lasts no longer than a few minutes during operation. In the current study, a novel architecture is provided for ECLDs that addresses this luminescence lifespan issue. The device architecture features an ECL active layer between two coplanar driving electrodes and a third floating bipolar electrode. The inclusion of the floating bipolar electrode enables modulating the electrical-field distribution within the active layer when a bias is applied between the driving electrodes. This, in turn, enables the use of opaque yet electrochemically stable noble metals as the driving electrodes while allowing ECL light to escape through the transparent floating bipolar electrode. A significant extension on operational lifetime is achieved, defined as the time required for the initial luminance (>100 cd m-2) to decrease by 50%, surpassing 1 h. This starkly contrasts the short lifetime (<1 min) attained by ECLDs in a conventional sandwich-type architecture with two transparent electrodes. These results provide simple strategies for developing durable ECL-based light-emitting devices.

Recent Advances in Electrochemiluminescence Biosensors for MicroRNA Detection.

Electrochemiluminescence (ECL) as an analytical technology with a perfect combination of electrochemistry and spectroscopy has received considerable attention in bioanalysis due to its high sensitivity and broad dynamic range. Given the selectivity of bio-recognition elements and the high sensitivity of the ECL analysis technique, ECL biosensors are powerful platforms for the sensitive detection of biomarkers, achieving the accurate prognosis and diagnosis of diseases. MicroRNAs (miRNAs) are crucial biomarkers involved in a variety of physiological and pathological processes, whose aberrant expression is often related to serious diseases, especially cancers. ECL biosensors can fulfill the highly sensitive and selective requirements for accurate miRNA detection, prompting this review. The ECL mechanisms are initially introduced and subsequently categorize the ECL biosensors for miRNA detection in terms of the quenching agents. Furthermore, the work highlights the signal amplification strategies for enhancing ECL signal to improve the sensitivity of miRNA detection and finally concludes by looking at the challenges and opportunities in ECL biosensors for miRNA detection.

Electrochemiluminescence Enhancement and Passivation Mitigation in Carbon Nitride Semiconductors via an Integrated Ternary Heterostructure Strategy.

In recent years, carbon nitride (CN) has attracted substantial attention in the field of electrochemiluminescence (ECL) applications, owing to its outstanding optical and electronic properties. However, the passivation of CN during the ECL process has contributed to reduced stability and poor repeatability. While some studies have tried to boost ECL performance by altering CN through doping and vacancies, effectively suppressing CN passivation at high potentials continues to be challenge. In this study, the built-in electric field and the Schottky barrier effect is used to expedite the transfer of electrons from CN to the molybdenum disulfide (MoS2) conduction band. This transfer deterred excessive electron injection into the CN band, thus mitigating its electrochemical degradation. Moreover, by introducing nickel nanoparticles (Ni NPs) as catalytic active sites, it is facilitated that the decomposition of potassium persulfate (K2S2O8), thereby enhancing both the stability and intensity of ECL emission. In the end, the application of ternary heterostructure as sensing platform for the cancer biomarker carcinoembryonic antigen (CEA) demonstrated high sensitivity. This research introduces a novel approach to overcome CN passivation, paving the way for more promising applications of CN in energy, environmental, and biosensing fields.

NiCo-LDH Hollow Nanocage Oxygen Evolution Reaction Promotes Luminol Electrochemiluminescence.

Conventional luminol co-reactant electrochemiluminescence (ECL) systems suffer from low stability and accuracy due to factors such as the ease of decomposition of hydrogen peroxide and inefficient generation of reactive oxygen species (ROS) from dissolved oxygen. Inspired by the luminol ECL mechanism mediated by oxygen evolution reaction (OER), the nickel-cobalt layered double hydroxide (NiCo-LDH) hollow nanocages with hollow structure and defect state are used as co-reaction promoters to enhance the ECL emission from the luminol-H2 O system. Thanks to the hollow structure and defect state, NiCo-LDH hollow nanocages show excellent OER catalytic activity, which can stabilize and efficiently produce ROS and enhance the ECL emission. Additionally, mechanistic exploration suggests that the ROS involved in the co-reaction of the luminol-H2 O system are derived from the OER reaction process, and there is a positive correlation between ECL intensity and the OER catalytic activity of the co-reaction promoter. The selection of catalysts with excellent OER catalytic activity is a key factor in improving ECL emission. Finally, a dual-mode immunosensor is constructed for the detection and analysis of alpha-fetoprotein (AFP) based on the promoting effect of NiCo-LDH hollow nanocages on the luminol-H2 O ECL system.

Aggregation-Induced Enhanced Electrochemiluminescence from Tris(bipyridine)ruthenium(II) Derivative Nanosheets for the Ultrasensitive Detection of Human Telomerase RNA.

The traditional tris(bipyridine)ruthenium(II) complex suffers from the notorious aggregation-caused quenching effect, which greatly compromises its electrochemiluminescence (ECL) efficiency, thus hindering further applications in biosensing and clinical diagnosis. Here, the ultrathin tetraphenylethylene-active tris(bipyridine)ruthenium(II) derivative nanosheets (abbreviated as Ru-TPE NSs) are synthesized through a protein-assisted self-assembly strategy for ultrasensitive ECL detection of human telomerase RNA (hTR) for the first time. The synthesized Ru-TPE NSs exhibit the aggregation-induced enhanced ECL behavior and excellent water-dispersion. Surprisingly, up to a 106.5-fold increase in the ECL efficiency of Ru-TPE NSs is demonstrated compared with the dispersed molecules in an organic solution. The restriction of intramolecular motions is confirmed to be responsible for the significant ECL enhancement. Therefore, this proposed ECL biosensor shows high sensitivity and excellent selectivity for hTR based on Ru-TPE NSs as efficient ECL beacons and the catalytic hairpin assembly as signal amplification, whose detection limit is as low as 8.0 fm, which is far superior to the previously reported works. Here, a promising analytical method is provided for early clinical diagnosis and a new type of efficient ECL emitters with great application prospects is represented.

C─H Activation Enables the Construction of New Bis-Polyaryl Phenylpyridine Ruthenium Complexes: Conjugation and Rigidity Synergistic Effect for Advanced Electrochemiluminescence.

The access to bench-stable organometallic compounds unfolds new chemical space for medicinal and material sciences. In particular, stable organoruthenium compounds with constitutional and stereoisomeric forms for subtle regulation of electrochemiluminescence are intriguing and challenging. Here, coordination of polycyclic aromatic hydrocarbons on (2-phenylpyridine)2(CO)2Ru complex allows access to bis-polyaryl phenylpyridine (BPP) Ruthenium complex through C─H activation strategy and coupling reactions for installation of the functionalities with steric and electronic purposes. The photoluminescence and electrochemiluminescence of BPP Ru complexes are affected by the actual polycyclic aromatic hydrocarbons inherent properties. The anthracene derivatized BPP Ru complex (BPP-Ant) shows the best ECL performance and reveals an enormous ECL quantum efficiency of 1.6-fold higher than the golden standard Ru(bpy)3 2+. The unprecedentedly high efficiency is due to the best compromise between the structural conjugation and molecular rigidity from BPP-Ant providing a providential energy gap that facilitated the feasibility of electron transfer and favored the radiative energy release by experimentally and DFT calculations. Moreover, PL and spooling ECL spectroscopies are used to track and link multiple emission peaks of BPP-Ant at 445, 645, and 845 nm to different emissive species. These discoveries will add a new member to the efficient ECL ruthenium complex family and bring more potentials.

Recent Advances in Electrochemiluminescence Visual Biosensing and Bioimaging.

Electrochemiluminescence (ECL) is one of the most powerful techniques that meet the needs of analysis and detection in a variety of scenarios, because of its highly analytical sensitivity and excellent spatiotemporal controllability. ECL combined with microscopy (ECLM) offers a promising approach for quantifying and mapping a wide range of analytes. To date, ECLM has been widely used to image biological entities and processes, such as cells, subcellular structures, proteins and membrane transport properties. In this review, we first introduced the mechanisms of several classic ECL systems, then highlighted the progress of visual biosensing and bioimaging by ECLM in the last decade. Finally, the characteristics of ECLM were summarized, as well as some of the current challenges. The future research interests and potential directions for the application of ECLM were also outlooked.

Glial fibrillary acidic protein, neurofilament light, matrix metalloprotease 3 and fatty acid binding protein 4 as non-invasive brain tumor biomarkers.

BACKGROUND: Gliomas are aggressive malignant tumors, with poor prognosis. There is an unmet need for the discovery of new, non-invasive biomarkers for differential diagnosis, prognosis, and management of brain tumors. Our objective is to validate four plasma biomarkers - glial fibrillary acidic protein (GFAP), neurofilament light (NEFL), matrix metalloprotease 3 (MMP3) and fatty acid binding protein 4 (FABP4) - and compare them with established brain tumor molecular markers and survival. METHODS: Our cohort consisted of patients with benign and malignant brain tumors (GBM = 77, Astrocytomas = 26, Oligodendrogliomas = 23, Secondary tumors = 35, Meningiomas = 70, Schwannomas = 15, Pituitary adenomas = 15, Normal individuals = 30). For measurements, we used ultrasensitive electrochemiluminescence multiplexed immunoassays. RESULTS: High plasma GFAP concentration was associated with GBM, low GFAP and high FABP4 were associated with meningiomas, and low GFAP and low FABP4 were associated with astrocytomas and oligodendrogliomas. NEFL was associated with progression of disease. Several prognostic genetic alterations were significantly associated with all plasma biomarker levels. We found no independent associations between plasma GFAP, NEFL, FABP4 and MMP3, and overall survival. The candidate biomarkers could not reliably discriminate GBM from primary or secondary CNS lymphomas. CONCLUSIONS: GFAP, NEFL, FABP4 and MMP3 are useful for differential diagnosis and prognosis, and are associated with molecular changes in gliomas.

Direct Comparative Studies Revealing the Contribution of TADF Activity of Organic Emitters Towards Efficient Electrochemiluminescence.

Electrochemiluminescence (ECL) featuring thermally activated delayed fluorescence (TADF) properties has attracted considerable interest, showcasing their potential for 100 % exciton harvesting, which marks a significant advancement in the realm of organic ECL. However, the challenge of elucidating the precise contribution of TADF to the enhanced ECL efficiency arises due to the lack of comparative studies of organic compounds with or without efficient TADF properties. In this study, we present four carbazole-benzonitrile molecules possessing similar chemical structures and comparable exchange energy (ΔEST). Despite their comparable properties, these compounds exhibited varying TADF efficiencies, warranting a closer examination of their underlying structural and electronic characteristics governing the optical properties. Consequently, intense ECL emission was only observed from 4CzBN with a remarkable TADF efficiency, underscoring the substantial difference in the ECL signal among molecules with comparable ΔEST and similar spectral properties but varying TADF activity.

Wireless Multimodal Light-Emitting Arrays Operating on the Principles of LEDs and ECL.

Electrochemistry-based light-emitting devices have gained considerable attention in different applications such as sensing and optical imaging. In particular, such systems are an interesting alternative for the development of multimodal light-emitting platforms. Herein we designed a multicolor light-emitting array, based on the electrochemical switch-on of light-emitting diodes (LEDs) with a different intrinsic threshold voltage. Thermodynamically and kinetically favored coupled redox reactions, i. e. the oxidation of Mg and the reduction of protons on Pt, act as driving force to power the diodes. Moreover, this system enables to trigger an additional light emission based on the interfacial reductive-oxidation electrochemiluminescence (ECL) mechanism of the Ru(bpy)3 2+/S2O8 2- system. The synergy between these light-emission pathways offers a multimodal platform for the straightforward optical readout of physico-chemical information based on composition changes of the solution.

High -Sensitive Detection of Malachite Green Based on Surface-Enhanced Electrochemiluminescence.

This article introduces a novel unlabeled surface-enhanced electrochemiluminescence (SEECL) sensor for malachite green (MG) detection. The SEECL sensor was prepared by modifying the Ru(bpy)32+ doped gold-SiO2 core-shell nanocomposites (Au@SiO2-Ru(bpy)32+) on the gold electrode. Ru(bpy)32+ of nanocomposites can not only emit electrochemiluminescence (ECL) with electrochemical reaction, but also induce the local surface plasmon resonance (LSPR) of gold core. That is beneficial to enhance the ECL signa of sensor. However, in the existence of MG, the luminescence of sensor would be quenched by the fluorescence resonance energy transfer (FRET) between MG and Ru(bpy)32+. In this paper, both fluorescence and ECL of the Au@SiO2-Ru(bpy)32+ were investigated for MG detection. And the results show that the SEECL sensor has high sensitive to MG. Under the optimal experimental conditions, the minimum detection concentration could be achieved about 1.0 nM of MG, which fully meets the China national standard detection requirements of veterinary drug residue in seafood.

Recent progress on charge transfer engineering in reticular framework for efficient electrochemiluminescence.

Electrochemiluminescence (ECL) is a luminescence production technique triggered by electrochemistry, which has emerged as a powerful analytical technique in bioanalysis and clinical diagnosis. During ECL, charge transfer (CT) is an important process between electrochemical excitation and luminescent emission, and dramatically affects the efficiency of exciton generation, playing a pivotal role in the light-emitting properties of nanomaterials. Reticular framework materials with intramolecular/intermolecular interactions offer a promising platform for regulating CT pathways and enhancing luminescence efficiency. Deciphering the role of intramolecular/intermolecular CT processes in reticular framework materials allows for the targeted design and synthesis of emitters with precisely controlled CT properties. This sheds light on the microscopic mechanisms of electro-optical conversion in ECL, propelling advancements in their efficiency and breakthrough applications. This mini-review focuses on recent advancements in engineering CT within reticular frameworks to boost ECL efficiency. We summarized strategies including intra-reticular charge transfer, CT between the metal and ligands, and CT between guest molecules and frameworks within reticular frameworks, which holds promise for developing next-generation ECL devices with enhanced sensitivity and light emission.

Electrochemiluminescent imaging of a NADH-based enzymatic reaction confined within giant liposomes.

Herein, transient releases either from NADH-loaded liposomes or enzymatic reactions confined in giant liposomes were imaged by electrochemiluminescence (ECL). NADH was first encapsulated with the [Ru(bpy)3]2+ luminophore inside giant liposomes (around 100 µm in diameter) made of DOPC/DOPG phospholipids (i.e., 1,2-dioleolyl-sn-glycero-3-phosphocholine/1,2-dioleoyl-sn-glycerol-3-phospho-(1'-rac-glycerol) sodium salt) on their inner- and outer-leaflet, respectively. Then, membrane permeabilization triggered upon contact between the liposome and a polarized ITO electrode surface and ECL was locally generated. Combination of amperometry, photoluminescence, and ECL provided a comprehensive monitoring of a single liposome opening and content release. In a second part, the work is focused on the ECL characterization of NADH produced by glucose dehydrogenase (GDH)-catalyzed oxidation of glucose in the confined environment delimited by the liposome membrane. This was achieved by encapsulating both the ECL and catalytic reagents (i.e., the GDH, glucose, NAD+, and [Ru(bpy)3]2+) in the liposome. In accordance with the results obtained, NADH can be used as a biologically compatible ECL co-reactant to image membrane permeabilization events of giant liposomes. Under these conditions, the ECL signal duration was rather long (around 10 s). Since many enzymatic reactions involve the NADH/NAD+ redox couple, this work opens up interesting prospects for the characterization of enzymatic reactions taking place notably in artificial cells and in confined environments.

Ratiometric electrochemiluminescence sensing and intracellular imaging of ClO- via resonance energy transfer.

Electrochemiluminescence resonance energy transfer (ECL-RET) is a versatile signal transduction strategy widely used in the fabrication of chem/biosensors. However, this technique has not yet been applied in visualized imaging analysis of intracellular species due to the insulating nature of the cell membrane. Here, we construct a ratiometric ECL-RET analytical method for hypochlorite ions (ClO-) by ECL luminophore, with a luminol derivative (L-012) as the donor and a fluorescence probe (fluorescein hydrazide) as the acceptor. L-012 can emit a strong blue ECL signal and fluorescein hydrazide has negligible absorbance and fluorescence signal in the absence of ClO-. Thus, the ECL-RET process is turned off at this time. In the presence of ClO-, however, the closed-loop hydrazide structure in fluorescein hydrazide is opened via specific recognition with ClO-, accompanied with intensified absorbance and fluorescence signal. Thanks to the spectral overlap between the ECL spectrum of L-012 and the absorption spectrum of fluorescein, the ECL-RET effect is gradually recovered with the addition of ClO-. Furthermore, the ECL-RET system has been successfully applied to image intracellular ClO-. Although the insulating nature of the cell itself can generate a shadow ECL pattern in the cellular region, extracellular ECL emission penetrates the cell membrane and excites intracellular fluorescein generated by the reactions between fluorescein hydrazide and ClO-. The cell imaging strategy via ECL-RET circumvents the blocking of the cell membrane and enables assays of intracellular species. The importance of the ECL-RET platform lies in calibrating the fluctuation from the external environment and improving the selectivity by using fluorescent probes. Therefore, this ratiometric ECL sensor has shown broad application prospects in the identification of targets in clinical diagnosis and environmental monitoring.

The tightest self-assembled ruthenium metal-organic framework combined with proximity hybridization for ultrasensitive electrochemiluminescence analysis of paraquat.

Metal-organic frameworks (MOFs), as porous materials, have great potential for exploring high-performance electrochemiluminescence (ECL) probes. However, the constrained applicability of MOFs in the realm of ECL biosensing is primarily attributed to their inadequate water stability, which consequently impairs the overall ECL efficiency. Herein, we developed a competitive ECL biosensor based on a novel tightest structural ruthenium-based organic framework emitter combining the proximity hybridization-induced catalytic hairpin assembly (CHA) strategy and the quenching effect between the Ru-MOF and ferrocene for detecting paraquat (PQ). Through a simple hydrothermal synthesis strategy, ruthenium and 2,2'-bipyrimidine (bpm) are head-to-head self-assembled to obtain a novel tightest structural Ru-MOF. Due to the metal-ligand charge-transfer (MLCT) effect between ruthenium and the bpm ligand and the connectivity between the internal chromophore units, the Ru-MOF exhibits strong ECL emissions. Meanwhile, the coordination-driven Ru-MOF utilizes strong metal-organic coordination bonds as building blocks, which effectively solves the problem of serious leakage of chromophores caused by water solubility. The sensitive analysis of PQ is realized in the range of 1 pg/mL to 1 ng/mL with a detection limit of 0.352 pg/mL. The tightest structural Ru-MOF driven by the coordination of ruthenium and bridging ligands (2,2'-bipyrimidine, bpm) provides new horizons for exploring high-performance MOF-based ECL probes for quantitative analysis of biomarkers.