Aggregation-induced Electrochemiluminescence Research Articles

Tetraphenylenthene-Based Conjugated Microporous Polymer for Aggregation-Induced Electrochemiluminescence.

We demonstrate the aggregation-induced electrochemiluminescence (AIECL) generated by 1,1,2,2-tetrakis(4-bromophenyl)ethane (TBPE)-based conjugated microporous polymers (TBPE-CMPs) and its biosensing application. We synthesized three TBPE-CMPs (i.e., TBPE-CMP-1, -2, -3) using three different molecules including tris(4-ethynylphenyl)amine (TEPA), 4,4'-diethynylbiphenyl (DEP), and 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine (TEPT). The TBPE-CMPs can act as electrochemiluminescence (ECL) emitters to generate AIECL. Among them, TBPE-CMP-1 exhibits the highest ECL efficiency (1.72%) due to the improved electron-hole recombination efficiency and efficient suppression of nonradiative transition. Moreover, the ECL properties of TBPE-CMPs can be tuned by the introduction of different conjugated molecules that can decrease the energy gap to facilitate the injection of an electron into the conjugated polymer backbone. Importantly, TBPE-CMP-1 can be used to construct an ECL sensor for the detection of dopamine, whose electro-oxidation products (e.g., leucodopaminechrome (LDC), dopaminechrome (DC), 5,6-dihydroxyindole (DHI), and 5,6-indolequinone (IDQ)) may function as energy acceptors to quench the ECL emission of TBPE-CMP-1. This ECL sensor exhibits high sensitivity and good anti-interference capability against ascorbic acid and uric acid.

Matrix Coordination-Induced Electrochemiluminescence Enhancement of Tetraphenylethylene-Based Hafnium Metal-Organic Framework: An Electrochemiluminescence Chromophore for Ultrasensitive Electrochemiluminescence Sensor Construction.

Here, we discovered that rigidifying the tetraphenylethylene (TPE)-based ligand H4TCBPE (H4TCBPE = 1,1,2,2-tetra(4-carboxylbiphenyl)ethylene) into Hf-based metal-organic framework (Hf-TCBPE) could lead to a stronger electrochemiluminescence (ECL) emission in comparison to H4TCBPE aggregates and H4TCBPE monomers. Due to the lack of close-packed TCBPE chromophores in Hf-TCBPE, which was required for aggregation-induced ECL (AI-ECL) enhancement, we defined this unprecedented phenomenon as matrix coordination-induced ECL (MCI-ECL) enhancement. The strong ECL intensity of Hf-TCBPE not only originated from the fixation of the TCBPE ligand between Hf6 clusters that restricted the intramolecular free motions of TCBPE and suppressed the nonradiative relaxation but also stemmed from the high porosity of Hf-TCBPE that rendered both internal and external TCBPE chromophores able to be excited. Considering the unique ECL characteristic of Hf-TCBPE, we combined the new ECL indicator of Hf-TCBPE as well as the phosphate-terminal ferrocene (Fc)-labeled hairpin DNA (Fc-HP3) aptamer together as a signal probe (Hf-TCBPE/Fc-HP3), which was employed to construct a novel "off-on" ECL sensor for ultrasensitive mucin 1 (MUC1) detection with the assistance of the exonuclease III (Exo III)-assisted recycling amplification strategy. As expected, the ECL sensor displayed a desirable linear response range from 1 fg/mL to 1 ng/mL and the detection limit down to 0.49 fg/mL. The MCI-ECL enhancement demonstrated by the Hf-TCBPE developed a new and promising strategy to design and synthesize high-performance metal-organic framework (MOF)-based ECL materials for constructing ultrasensitive ECL sensors.

Multifunctional Zinc Oxide Promotes Electrochemiluminescence of Porphyrin Aggregates for Ultrasensitive Detection of Copper Ion.

The design and exploration of highly efficient organic luminophores for an electrochemiluminescence (ECL) sensor is a fascinating and promising subject. Herein, we present a surfactant-assisted self-assembly of 5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin (TCPP) J-aggregate as a robust organic luminophore to construct the solid-state ECL sensing platform with significantly enhanced and constantly stable signals, by using peroxydisulfate (S2O82-) as the coreactant, and l-cysteine capped zinc oxide nanoflowers (ZnO@Cys NFs) as the multifunctional energy donor and coreactant accelerator. Compared with TCPP monomer, this TCPP J-aggregate possesses a unique aggregation-induced electrochemiluminescence (AIECL) performance, which results in 5-fold enhancement in red-light ECL emission at 675 nm. The resonance energy transfer from the ZnO@Cys NFs (energy donor) to the TCPP J-aggregate (energy acceptor) substantially improves the ECL intensity and stability. ZnO@Cys NFs have also been used as a coreactant accelerator to promote the conversion of more S2O82- into SO4•-. The corresponding ECL mechanism has been investigated by UV-vis absorption spectrum, photoluminescence, ECL, and density functional theory. Since l-cysteine on ZnO@Cys NFs can efficiently realize bidentate chelation with Cu2+, the proposed ECL sensor shows a highly selective and sensitive quenching effect for the detection of Cu2+ with a wide linear range from 1.0 pmol·L-1 to 500 nmol·L-1 and a detection limit of 0.33 pmol·L-1, paving a bright research direction for the development of TCPP aggregates in ECL field.

Highly Efficient Aggregation-Induced Electrochemiluminescence of Polyfluorene Derivative Nanoparticles Containing Tetraphenylethylene.

SummaryThe aggregation-induced electrochemiluminescence (AIECL) of polyfluorene derivative nanoparticles containing tetraphenylethylene (TPE) in aqueous media is reported in this work. The TPE unit limits the intramolecular free rotation of phenyl rings, as well as the π-π stacking interactions of molecules, which significantly enhances ECL signal of the polyfluorene nanoparticles. With co-reactants of tri-n-propylamine (TPrA) and S2O82−, the copolymer nanoparticles show visualized ECL emissions at both positive and negative potentials. The ECL efficiency of copolymer nanoparticles in solid state is 163% compared with that of standard ECL species, Ru(bpy)32+. And at negative potential, the ECL intensity of copolymer nanoparticles is even stronger with 6.5 times compared with that at positive potential. The ECL generation mechanisms are analyzed detailed by annihilation and co-reactant route transient ECL test (millisecond scale). This work provides a reference for the organic structure design for AIECL and shows promising potential in luminescent device and biological applications.

Dual Enhancement of Gold Nanocluster Electrochemiluminescence: Electrocatalytic Excitation and Aggregation-Induced Emission.

Ligand-protected gold nanoclusters (AuNCs) have emerged as a new class of electrochemiluminescence (ECL) luminophores for their interesting catalytic and emission properties, although their quantum yield (ΦECL ) in aqueous medium is low with a poor mechanistic understanding of the ECL process. Now it is shown that drying AuNCs on electrodes enabled both enhanced electrochemical excitation by an electrocatalytic effect, and enhanced emission by aggregation-induced ECL (AIECL) for 6-aza-2-thiothymine (ATT) protected AuNCs with triethylamine (TEA) as a coreactant. The dried ATT-AuNCs/TEA system resulted in highly stable visual ECL with a ΦECL of 78 %, and a similar enhancement was also achieved with methionine-capped AuNCs. The drying enabled dual-enhancement mechanism has solved a challenging mechanistic problem for AuNC ECL probes, and can guide further rational design of ECL emitters.

Dual Enhancement of Gold Nanocluster Electrochemiluminescence: Electrocatalytic Excitation and Aggregation‐Induced Emission

AbstractLigand‐protected gold nanoclusters (AuNCs) have emerged as a new class of electrochemiluminescence (ECL) luminophores for their interesting catalytic and emission properties, although their quantum yield (ΦECL) in aqueous medium is low with a poor mechanistic understanding of the ECL process. Now it is shown that drying AuNCs on electrodes enabled both enhanced electrochemical excitation by an electrocatalytic effect, and enhanced emission by aggregation‐induced ECL (AIECL) for 6‐aza‐2‐thiothymine (ATT) protected AuNCs with triethylamine (TEA) as a coreactant. The dried ATT‐AuNCs/TEA system resulted in highly stable visual ECL with a ΦECL of 78 %, and a similar enhancement was also achieved with methionine‐capped AuNCs. The drying enabled dual‐enhancement mechanism has solved a challenging mechanistic problem for AuNC ECL probes, and can guide further rational design of ECL emitters.

Recent Advances in Aggregation-Induced Electrochemiluminescence.

The emergence of the rising alliance between aggregation-induced emission (AIE) and electrochemiluminescence (ECL) is defined as aggregation-induced electrochemiluminescence (AIECL). The booming science of AIE has proved to be not only distinguished in luminescent materials but could also inject new possibility into ECL analysis. Especially in the aqueous phase and solid state for hydrophobic materials, AIE helps ECL circumvent the dilemma between substantial emission intensity and biocompatible media. The wide range of analytes makes ECL an overwhelmingly interesting analytical technique. Therefore, AIECL has gained potential in clinical diagnostics, environmental assays, and biomarker detections. This review will focus on introduction of the novel concept of AIECL, current applied luminophores, and related applications developed in recent years.

Aggregation-Induced Electrochemiluminescence by Metal-Binding Protein Responsive Hydrogel Scaffolds.

Functionalized hydrogels have aroused general interest due to their versatile applications in biomaterial fields. This work reports a hydrogel network composed of gold nanoclusters linked with bivalent cations such as Ca2+ , Mg2+ , and Zn2+ . The hydrogel exhibits both aggregation-induced emission (AIE) and aggregation-induced electrochemiluminescence (AIECL) effects. Most noteworthy, the AIECL effect (≈50-fold enhancement) is even more significant than the corresponding AIE effect (approximately fivefold enhancement). Calmodulin, a Ca2+ binding protein, may efficiently regulate the AIECL dynamics after specific binding of the Ca2+ linker, with the linear range from 0.3 to 50 µg mL-1 and a limit of detection of 0.1 µg mL-1 . Considering the important roles of bivalent cations in the life system, these results may pave a new avenue for the design of a biomolecule-responsive AIECL-type hydrogel with multifunctional biomedical purposes.

An aptasensor for troponin I based on the aggregation-induced electrochemiluminescence of nanoparticles prepared from a cyclometallated iridium(III) complex and poly(4-vinylpyridine-co-styrene) deposited on nitrogen-doped graphene.

An ultrasensitive electrochemiluminescence (ECL) disposable aptamer sensor (aptasensor) is presented for detection of myocardial infarction biomarker by quantification of troponin I in blood serum. A screen-printed electrode was modified with (a) aptamer-modified gold nanoparticles, (b) cyclometallated iridium(III)-poly-4-vinylpyridine nanoparticles, and (c) nitrogen-doped graphene in order to increase the loading capacity and conductivity of the aptasensor. If the aptasensor is exposed to troponin I, it will bind to the aptamer and desorb the aptamer from gold nanoparticles and the surface of the electrode. This generates an enhancement in ECL emission depending on troponin I concentration. ECL emission is strongly improved by aggregation-induced phenomenon, which is caused by inhibition of the water and oxygen quenching effect on the iridium complex ECL in aqueous media. Under optimum conditions, the aptasensor has a wide dynamic range that extends from 0.1 pM to 10nM, with a 20 fM detection limit (S/N = 3) and a relative standard deviation of 3.1%. The ECL aptasensor was successfully applied to 20 individual human serum for the detection of troponin I biomarker. Graphical abstract Schematic presentation of electrochemiluminescence aptamer assay fabrication for detection of Troponin I. Carbon screen printed electrode (CSPE) was modified with nitrogen doped graphene (NG), gold nanoparticles (AuNPs), cyclometallated iridium(III)-polyvinylpyridine polymer nanoparticles, ionic liquid and bovine serum albumin.

Aggregation-Induced Electrochemiluminescence of Carboranyl Carbazoles in Aqueous Media.

The aggregation-induced electrochemiluminescence (AIECL) of carboranyl carbazoles in aqueous media was investigated for the first time. Quantum yields, morphologies, and particle sizes were observed to determine the electrochemiluminescence (ECL) performance of these aggregated organic dots (ODs). All compounds exhibit much higher ECL stability and intensity than the carborane-free compound, demonstrating the essential role of the carboranyl motif. Moreover, the results of cyclic voltammetry (CV) suggest that oxidation/reduction reactions take place at the carboranyl motif. The excited states of ODs were proposed to be generated by the mechanism of surface state transitions. More importantly, these compounds show a reductive-oxidative mechanism in contrast to other organic materials that show oxidative-reductive mechanisms. Our experiments and data have established the relation between AIE organic structures and ECL properties that has a strong potential for biological and diagnostic applications.

Aggregation‐Induced Electrochemiluminescence of Carboranyl Carbazoles in Aqueous Media

AbstractThe aggregation‐induced electrochemiluminescence (AIECL) of carboranyl carbazoles in aqueous media was investigated for the first time. Quantum yields, morphologies, and particle sizes were observed to determine the electrochemiluminescence (ECL) performance of these aggregated organic dots (ODs). All compounds exhibit much higher ECL stability and intensity than the carborane‐free compound, demonstrating the essential role of the carboranyl motif. Moreover, the results of cyclic voltammetry (CV) suggest that oxidation/reduction reactions take place at the carboranyl motif. The excited states of ODs were proposed to be generated by the mechanism of surface state transitions. More importantly, these compounds show a reductive–oxidative mechanism in contrast to other organic materials that show oxidative–reductive mechanisms. Our experiments and data have established the relation between AIE organic structures and ECL properties that has a strong potential for biological and diagnostic applications.

Electrochemiluminescence Enhanced by Restriction of Intramolecular Motions (RIM): Tetraphenylethylene Microcrystals as a Novel Emitter for Mucin 1 Detection.

Apart from the reported energy transfer mechanism of aggregation-induced electrochemiluminescence (AI-ECL) enhancement, a new strategy named restriction of intramolecular motions-driven ECL (RIM-ECL) enhancement is first proposed based on the phenomenon of a very strong electrochemiluminescence observed on the hexagonal tetraphenylethylene microcrystals (TPE MCs) in aqueous solution. Compared to TPE in molecule-isolation state with faint ECL, TPE in aggregate state (TPE MCs) showed a significantly enhanced ECL that was due to the restriction of intramolecular motions (RIM). Inspired by the unique luminescence characteristic of TPE MCs, we integrated the novel ECL emitter of TPE MCs and target-activated bipedal DNA walker together to fabricate a sensitive "off-on" ECL biosensor for Mucin 1 (MUC1) assay, which exhibited desirable linear response for a concentration scope from 1 fg/mL to 1 ng/mL with a low detection limit of 0.29 fg/mL. The RIM enhanced ECL demonstrated by the TPE MCs provides a new chapter in the exploration of aggregated organic emitters for further applications.

Aggregation-Induced Electrochemiluminescence from a Cyclometalated Iridium(III) Complex.

Aggregation-induced emission has been extensively found in organic compounds and metal complexes. In contrast, aggregation-induced electrochemiluminescence (AI-ECL) is rarely observed. Here, we employ two tridentate ligands [2,2':6',2″-terpyridine (tpy) and 1,3-bis(1 H-benzimidazol-2-yl)benzene (bbbiH3)] to construct a cyclometalated iridium(III) complex, [Ir(tpy)(bbbi)] (1), showing strong AI-ECL. Its crystal structure indicates that neighboring [Ir(tpy)(bbbi)] molecules are connected through both π-π-stacking interactions and hydrogen bonds. These supramolecular interactions can facilitate the self-assembly of complex 1 into nanoparticles in an aqueous solution. The efficient restriction of molecular vibration in these nanoparticles leads to strong AI-ECL emission of complex 1. In a dimethyl sulfoxide-water (H2O) mixture with a gradual increase in the H2O fraction from 20% to 98%, complex 1 showed a ∼39-fold increase in the electrochemiluminescence (ECL) intensity, which was ∼4.04 times as high as that of [Ru(bpy)3]2+ under the same experimental conditions. Moreover, the binding of bovine serum albumin to the nanoparticles of complex 1 can improve the ECL emission of this complex, facilitating the understanding of the mechanism of AI-ECL for future applications.

Aggregation-Induced Electrochemiluminescence of Platinum(II) Complexes.

We report the electrochemiluminescence properties of square-planar Pt(II) complexes that result from the formation of supramolecular nanostructures. We define this new phenomenon as aggregation-induced electrochemiluminescence (AIECL). In this system, self-assembly changes the HOMO and LUMO energies, making their population accessible via ECL pathways and leading to the generation of the luminescent excited state. Significantly, the emission from the self-assembled system is the first example of electrochemiluminescence (ECL) of Pt(II) complexes in aqueous solution having higher efficiency than the standard, Ru(bpy)32+.The finding can lead to a new generation of bright emitters that can be used as ECL labels.