Li Fu

Screening a novel electrochemiluminescence (ECL) system with enhanced ECL efficiency is crucial to ECL evolution. Aggregation-induced short-chain Au nanoclusters (AuNCs) are an intriguing strategy to tune their ECL properties. However, achieving superior ECL efficiency involving an aggregation-induced strategy of long-chain stabilizer-capped AuNCs in aqueous phase remains a formidable challenge. Herein, the high ECL efficiency of AuNCs was synthesized from Zn²⁺-mediated aggregation-induced AuNCs involved in short/long chain ligands including d-penicillamine/11-mercaptoundecanoic acid (d-DPA/MUA) as dual stabilizers and tert-butylamine borane as reductant (Zn²⁺-d-DPA/MUA@AuNCs). Specifically, the formation of aggregation-induced superstructures resulted in nearly complete quenching of vibrations and dipole moments of the -CH₂- moieties in MUA, which was attributed to the conformational contraction of the overall structure and constrained intramolecular motion. Moreover, with the addition of Zn²⁺ into the d-DPA/MUA@AuNCs, the morphology of spheroidal assembled structure grew up, the carrier concentration of the AuNCs increased, the electron-hole recombination at the interface was promoted, and thus the carrier separation efficiency decreased. This was beneficial to the enhanced NIR (beyond 800 nm) ECL around 9-fold compared with Zn-free AuNCs. Zn²⁺-d-DPA/MUA@AuNCs were utilized as a probe for the detection of prostate-specific antigen (PSA) in the linear concentration range 5-800 ng/mL with a limit of detection of 1 ng/mL (S/N = 3) with ECL image and wavelength-based intensity dual mode.

Schematic diagram of the strategies used for LTP ECL.

Screening a novel electrochemiluminescence (ECL) system and lowering the ECL triggering potential are essential to ECL evolution. Herein, the near-infrared (NIR) ECL system with low-triggering potential ECL was constructed with weakly reductive tert-butylamine borane as coreactant and mercaptosuccinic acid/citrate (MSA/Cit)-capped Au (MSA/Cit@AuNCs) as luminophores. Toxic-element-free and dual-ligand MSA/Cit@AuNCs were prepared via ligand exchange and utilized as a model for developing unary metal NCs-based luminophores with more enhanced ECL performance than monoligand Au nanocrystals (AuNCs), which exhibited a two hole-injected process at around 0.48 and 0.80 V, respectively. Beneficial to the intrinsic low hole-injected potential of AuNCs, MSA/Cit@AuNCs exhibited similar low-triggering ECL potential at around 0.57 V with the participation of series coreactants or not, originating from the recombination of an internal prestored electron within the conduction band (CB) and electroinjected holes at around 0.25 V. Furthermore, the enhanced low-triggering potential around 0.57 V and NIR ECL around 835 nm of MSA/Cit@AuNCs was eventually obtained with the reductive tert-butylamine borane or N₂H₄·H₂O containing a -C-N single-bond structure merely as coreactant. The low-triggering potential ECL of MSA/Cit@AuNCs/tert-butylamine borane system at 0.57 V can be harnessed to selectively determine a carcinoembryonic antigen (CEA) with one linear range spanning from 2 to 20000 fg/mL and a limit of detection of 0.33 fg/mL (S/N = 3). This study will contribute to a more comprehensive understanding of the ECL mechanism in terms of both regulating NCs and selecting coreactants.

The electrochemiluminescence (ECL) bioassay is prominently carried out with the involvement of the coreactant. To remove the detrimental effects of the coreactant on the ECL of luminophores, herein, a promising ECL immunoassay strategy with biocompatible nanoparticles as the luminophore is proposed, which involves directly and electrochemically oxidizing the luminophore methionine-capped Au (Met@Au) nanocrystals (NCs) without the participation of any coreactant. Met@Au NCs are a kind of n-type nanoparticles, and they can be electrochemically injected with valence band (VB) holes around +0.80 and +1.10 V (vs Ag/AgCl). The electrochemically injected exogenous VB hole can recombine with the endogenous conduction band electron of Met@Au NCs and eventually bring out two coreactant-free and near-infrared ECL processes around 0.80 V (ECL-1) and 1.10 V (ECL-2). The intensity of coreactant-free ECL is primarily determined by the electrochemical oxidation-induced hole-injection process. ECL-2 is considerably stronger than ECL-1 and can be exploited for determining the carcinoembryonic antigen (CEA) in a sandwich immunoassay procedure with a linear range from 0.1 to 50 pg/mL as well as a limit of detection of 0.03 pg/mL (S/N = 3).

The photoluminescence, electroluminescence, and electrochemiluminescence from nanocrystals (NCs) have been extensively exploited for both fundamental and applied investigation over two decades, while the understanding of chemiluminescence (CL) from NCs is still far from clear by now. Herein, a general route for triggering CL from NC luminophore is proposed by extensively exploiting the charge transfer between n-type NCs and oxidants. Oxidants, such as K₂S₂O₈, H₂O₂, KMnO₄, and NaClO, can chemically inject the hole onto the valence band (VB) of methionine-capped n-type AuNCs (Met@AuNCs) and enable the occurrence of efficient radiative-charge-recombination between the chemically injected exogenous VB hole and the pre-existed endogenous conduction band (CB) electron, which eventually results in single-color and defect-involved CL with the maximum emission wavelength around 824 nm. The CL of Met@AuNCs/oxidant is qualified for ultrasensitive CL immunoassay in a similar procedure to the biotin-avidin and magnetic separation involved commercial CL immunoassay and exhibits acceptable performance for linearly determining carcinoembryonic antigen from 50 pg/mL to 100 ng/mL with a limit of detection of 10 pg/mL (S/N = 3). This strategy provides a general route to develop nanoparticulate CL luminophores and might eventually enable CL multiplexing assay via extensively exploiting the CL of different wavebands.

All commercial chemiluminescence (CL) assays are conducted with either glow or flash CL of eye-visible waveband from chemical luminophores. Herein, glow and flash, as well as waveband adjustable CL from the same nanoparticle luminophore of thiol-capped CuInS₂@ZnS nanocrystals (CIS@ZnS-Thiol), are proposed via extensively exploiting the differed redox nature of CL triggering reagents. Taking thiosalicylic acid (TSA) as the model thiol-capping agent, the electron-injection-initiated charge transfer between CIS@ZnS-TSA and reductant can bring out efficient glow CL while the hole-injection-initiated charge transfer between CIS@ZnS-TSA and oxidant can give off obvious flash CL under optimum conditions. The maximum emission wavelength for CL of CIS@ZnS-TSA is adjustable from 730 nm to 823 nm via employing different triggering agents. Promisingly, the coexistent reductant of N₂H₄·H₂O and oxidant of H₂O₂ can be employed as dual triggering reagents to trigger eye-visible and highly efficient flash CL from CIS@ZnS-TSA. The maximum emission intensity for flash CL of CIS@ZnS-TSA/N₂H₄-H₂O₂ is 101-fold greater than the glow CL of CIS@ZnS-TSA/N₂H₄ and 22-fold greater than the flash CL of CIS@ZnS-TSA/H₂O₂, respectively. The flash CL from CIS@ZnS-TSA/N₂H₄-H₂O₂ is qualified for highly sensitive and selective CL immunoassay in a commercialized typical procedure with the entire operating process manually terminated within 35 min.

The intensity of electrochemiluminescence (ECL) usually changes rapidly with the progress of the electrochemical process, making it difficult to determine the ECL spectrum with a conventional photomultiplier in a wavelength scan model. Herein, a band-pass filter (BPF)-involved modulating strategy is proposed to upgrade a conventional ECL analyzer to a highly sensitive ECL spectrometer without changing its hardware. The ECL spectrum can be figured out by rapidly and/or continuously modulating a part of the ECL intensity–time curve with a BPF array of different central wavelengths as well as correcting the ECL intensity at different measurement times by a univariate cubic polynomial model. This strategy not only can determine the spectrum of ultra-weak emission with high sensitivity via merely modulating the emission within a short period, including the weak self-ECL from either Ru(bpy)₃²⁺ or tripropylamine (TPA), but also can demonstrate the interaction between the co-existing emitters. It is shown that the ECL from both Ru(bpy)₃²⁺ and TPA of the Ru(bpy)₃²⁺/TPA system can be mutually promoted in electrochemical potential and in a concentration-dependent way. The self-ECL of TPA at the potential of 1.24 V can be enhanced from 4.9- to 51-fold with the Ru(bpy)₃²⁺ concentration increasing from 0.01 to 0.8 μM. In the presence of 0.04 μM Ru(bpy)₃²⁺, the self-ECL of TPA is enhanced by 94- and 10.2-fold at the potential of 1.01 and 1.76 V, respectively. The portable inexpensive BPF turntable device is also useful in spectrum-resolved multi-analyte determination and ratiometric ECL biosensors.