Cluster-Dominated Electrochemiluminescence of Tertiary Amines in Polyethyleneimine Nanoparticles: Mechanism Insights and Sensing Application.

Designing and screening highly efficient and cost-effective luminophores have always been a challenge to develop sensitive electrochemiluminescence (ECL) biosensors. Herein, polyethyleneimine nanoparticles (PEI NPs), a kind of nonconjugated polymer (NCP) NPs with tertiary amine clusters, were developed as an ECL luminophore. Specifically, PEI NPs were synthesized by a one-step hydrothermal method using PEI and formaldehyde. The properties of PEI NPs were investigated in detail using photochemical and electrochemical techniques. The results showed cluster-dominated luminescence of tertiary amines in PEI NPs via "through-space conjugation". This non-negligible ECL performance (at 631 nm) was also verified by the initiated reduction-oxidation process. With persulfate as a coreactant, PEI NPs acted as both the luminophore and coreaction accelerator to enhance the ECL intensity remarkably, which was eightfold higher than that of isolated PEI. Moreover, choosing dopamine as the model target, a highly sensitive "signal off" ternary ECL sensor was constructed utilizing PEI NPs as the luminophore. Dopamine could be oxidized to benzoquinone at the sensing interface, quenching the signal via ECL energy transfer. Free from any signal amplification, the proposed sensor achieved a low detection limit (4.3 nM) for target monitoring with good selectivity and stability. This strategy not only provides a unique perspective for designing novel efficient and facile ECL luminophores of tertiary amines but also broadens the biological application of NCP NPs.

High-performance assaying cardiac troponin I using Bi-doped tin-based heterojunction in photoelectrochemical biosensing with the quencher of yolk-shell nanostructure.

Cardiac troponin I (cTnI), a protein regulating myocardial contraction, stands the premier biomarker for diagnosing acute myocardial infarction and stratifying heart disease risk. Photoelectrochemical (PEC) biosensing combines traditional PEC analysis with high bioconjugation specificity, rendering a prospective avenue for disease biomarker analysis. However, the performance of sensors often falls short due to inadequate photoelectric materials. Hence, designing heterojunctions with proper band alignment, effective transport and separation of photogenerated carriers is highly expected for PEC sensors. Meanwhile, doping as a synergistic strategy to tune the energy band edges and improve carrier transport in heterojunctions, can also enhance the sensing performance. In this work, bismuth-doped tin oxide and tin disulfide heterojunction (Bi-SnOS) was prepared via a simple one-step hydrothermal method and utilized as a highly sensitive platform. Integrating copper sulfide-coated nano-gold (Au@CuS), a yolk-shell shaped nanocomposites, as the double quenching probe, an excellent PEC biosensor was fabricated to assay cTnI via sandwich immunorecognition. Under optimal conditions, the proposed biosensor displayed a high-performance for cTnI in the range from 0.1 pg/mL to 5.0 ng/mL with a low detection limit (44.7 fg/mL, 3σ). The strong photocurrent response, high stability and suitable selectivity point out that the synergistic effect between heterojunction and doping provides a promising prospect for the design of new PEC materials.

Novel electrochemiluminescence luminophore based on flower-like binuclear coordination polymer for high-sensitivity detection of tetracycline in food products.

To meet the growing concerns about food safety, sensors for tetracycline antibiotics have been urgently needed. Herein, we synthesized a series of binuclear coordination polymers (Tb-Zn-CPs) based on lanthanide and transition metal ions by solvothermal method using [1,1':4',1''-terphenyl]-3,3'',5,5''-tetracarboxylic acid, Tb(NO3)3 and Zn(NO3)2. The morphologies and electrochemiluminescence (ECL) performances of Tb-Zn-CPs varied with different molar ratios of terbium and zinc ions (Tb:Zn). The flower-like Tb-Zn-CP (9:3) possessed the highest ECL intensity due to the ligand antenna effect and the sensitization of Zn2+. An ECL sensor for the detection of tetracycline (TC) was constructed utilizing Tb-Zn-CP (9:3) as a novel ECL luminophore and potassium persulfate as a coreactant. The proposed sensor achieved sensitive detection of TC in the range of 5.0 fmol·L-1 to 3.0 mmol·L-1 with a low limit of detection (1.6 fmol·L-1). It also was applied for TC detection in dairy products with good recovery rates.