Search

Metal nanoclusters (NCs) as a new kind of luminophore have acquired sufficient interest, but their widespread application is restricted on account of their relatively low electrochemiluminescence (ECL) efficiency. Then, aqueous metal NCs with high ECL efficiency were strongly anticipated, especially for the ultrasensitive analysis of biomarkers. Herein, a near-infrared (NIR) ECL biosensing strategy for the test of neuron-specific enolase (NSE) was proposed by utilizing N -acetyl-l-cysteine (NAC)- and cysteamine (Cys)-stabilized gold NCs (NAC/Cys-AuNCs) as ECL emitters with the NIR ECL emission around 860 nm and a metal-organic framework/palladium nanocubes (ZIF-67/PdNCs) hybrid as the coreaction accelerator through their admirable electrocatalytic activity. The NIR emission would reduce photochemical injury to the samples and even realize nondestructive analysis with highly strong susceptibility and suitability. Furthermore, the utilization of ZIF-67/PdNCs could improve the ECL response of NAC/Cys-AuNCs by facilitating the oxidation of the coreactant triethylamine (TEA), leading to the production of a larger quantity of reducing intermediate radical TEA •+ . Consequently, NAC/Cys-AuNCs with ZIF-67/PdNCs displayed 2.7 fold enhanced ECL emission compared with the single NAC/Cys-AuNCs using TEA as the coreactant. In addition, HWRGWVC (HWR), a heptapeptide, was introduced to immobilize antibodies for the specially binding Fc fragment of the antibodies, which improved the binding efficiency and sensitivity. As a result, a "signal-on" immunosensor for NSE analysis was obtained with an extensive linear range of 0.1 to 5 ng/mL and a low limit of detection (0.033 fg/mL) (S/N = 3). This study provides a wonderful method for the development of an efficient nondestructive immunoassay.

The unique optoelectronic and tunable luminescent characteristics of copper nanoclusters (Cu NCs) make them extremely promising as luminophores. However, the limited luminescence intensity and stability of Cu NCs have restricted their application in the field of electrochemiluminescence (ECL). Herein, a self-assembly-induced enhancement strategy was successfully employed to enhance the cathodic ECL performance of flexible ligand-stabilized Cu NCs. Specifically, Cu NCs form ordered sheetlike structures through intermolecular force. The restriction of ligand torsion in this self-assembled structure leads to a significant improvement in the ECL properties of the Cu NCs. Experimental results demonstrate that the assembled nanoscale Cu NC sheets exhibit an approximately three-fold increase in cathodic ECL emission compared to the dispersed state of Cu NCs. Furthermore, assembled nanoscale Cu NCs sheets were utilized as signal probes in conjunction with a specific short peptide derived from the catalytic structural domain of matrix metalloproteinase 14 (MMP 14) as the identification probe, thereby establishing a split-type ECL sensing platform for the quantification of NMP 14. The investigation has revealed the exceptional performance of assembled nanoscale Cu NCs sheets in ECL analysis, thus positioning them as novel and promising signal probes with significant potential in the field of sensing.

Nowadays, continuous efforts have been devoted to searching highly efficient electrochemiluminescence (ECL) emitters for applications in clinical diagnosis and food safety. In this work, triazinyl-based hydrogen bond organic frameworks (Tr-HOFs) were synthesized by N···H hydrogen bond self-assembly aggregation, where 6,6'-(1,4-phenylene)bis(1,3,5-triazine-2,4-diamine) (phenyDAT) was prepared via the cyclization reaction and behaved as a novel ligand. Impressively, the resulting Tr-HOFs showed strong ECL responses with highly enhanced ECL efficiency (21.3%) relative to the Ru(bpy) 3 2+ standard, while phenyDAT hardly showed any ECL emission in aqueous phase. The Tr-HOFs innovatively worked as a new ECL luminophore to construct a label-free biosensor for assay of kanamycin (Kana). Specifically, the ECL response greatly weakened upon assembly of captured DNA with ferrocene (cDNA-Fc) onto the Tr-HOFs-modified electrode, while the ECL signals were adversely recovered by releasing linked DNA (L-DNA) from double-stranded DNA (dsDNA, hybridization of aptamer DNA (aptDNA) with L-DNA) due to the specific recognition of Kana with the aptDNA combined by the linkage of L-DNA and cDNA-Fc on the electrode. The as-built sensor showed a broadened linear range (1 nM-10 μM) and a limit of detection (LOD) down to 0.28 nM, which also displayed satisfactory results in the analysis of Kana in the milk and diluted human serum samples. This work offers a novel pathway to design an ECL emitter with organic molecules, holding great promise in biomedical analysis and food detection.

Based on the necessity and urgency of detecting infectious disease marker procalcitonin (PCT), a novel unlabeled photoelectrochemical (PEC) immunosensor was prepared for the rapid and sensitive detection of PCT. Firstly, SnO 2 porous nanoflowers with good photocatalytic performance were prepared by combining hydrothermal synthesis and calcining. BiOI nanoflowers were synthesized by facile ultrasonic mixed reaction. Ag 2 S quantum dots were deposited on SnO 2 /BiOI composites by in situ growth method. The SnO 2 /BiOI/Ag 2 S composites with excellent photoelectric properties were employed as substrate material, which could provide significantly enhanced and stable signal because of the energy level matching of SnO 2 , BiOI and Ag 2 S and the good light absorption performance. Accordingly, a PEC immunosensor based on SnO 2 /BiOI/Ag 2 S was constructed by using the layered modification method to achieve high sensitivity analysis of PCT. The linear dynamic range of the detection method was 0.50 pg·mL -1 ~100 ng·mL -1 , and the detection limit was 0.14 pg·mL -1 . In addition, the designed PEC immunosensor exhibited satisfactory sensitivity, selectivity, stability and repeatability, which opened up a new avenue for the analyzation of PCT and further provided guidance for antibiotic therapy.

Integrating a microfluidic sensor with a ratiometric photoelectrochemical (PEC) strategy to build a bioanalysis device for actual sample testing is often limited to large-volume space-resolution equipment and wavelength-dependent or potential-dependent paired photoactive materials. This work reports a microfluidic ratiometric magnetic-photoelectrochemical (M-PEC) biosensor on the photochromic composite platform to solve the above problems. In particular, as a proof-of-concept study, the platform Bi 2 WO 6- x /amorphous BiOCl nanosheets/Bi 2 S 3 (p-BWO-s) mediated by photochromic color centers and the magnetic photoactive secondary antibody marker ZnFe 2 O 4 @Ag 2 O are integrated on the microfluidic biosensor. By enhancement of the photochromic color centers, p-BWO-s outputs a considerable photocurrent signal. Meanwhile, the photoactivity of the secondary antibody marker can be changed with a magnetic field; thus, different photocurrent signals can be obtained to realize ratiometric detection. The quenching photocurrent signal without the magnetic field and the difference photocurrent signal under the magnetic field are quantitatively related to the target concentration, which unfolds a novel general strategy for bioanalysis. Different from traditional ratiometric PEC biosensors, this work characterizes the first ratiometric PEC biosensor based on an external magnetic field. Generally speaking, combined with different biorecognition cases, this scheme with good expansibility brings a unique new perspective.

In this study, a sensitive label-free electrochemical immunosensor was designed based on nanoporous Fe3O4 and a biotin-streptavidin system to specifically detect zearalenone (ZEN). Herein, nanoporous Fe3O4 was employed to carry streptavidin to prepare the highly sensitive immunosensor. The application of nanoporous Fe3O4 and the biotin-streptavidin reaction provided large amounts of antibodies on each conjugate, thus amplifying the detected signal. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were conducted to characterize the modification with ZEN. Factors which might influence the properties of the immunosensor, including concentration of nanoporous Fe3O4, pH of the buffer, incubation time and temperature were studied. Under the best conditions, the immunosensor displayed a highly sensitive response toward ZEN, ranging in concentration from 10.0 pg mL-1 to 3.00 ng mL-1 and 3.00 ng mL-1 to 12.0 ng mL-1, with a low detection limit of 3.7 pg mL-1. The results for analysis of human urine samples were satisfactory. Furthermore, this proposed method may find promising applications in the detection of other mycotoxins.

An ultrasensitive label-free photoelectrochemical (PEC) immunosensor was developed to detect amyloid β-protein (Aβ) based on CdS/CdTe-cosensitized SnO2 nanoflowers. Specifically, SnO2 with a flower-like porous nanostructure was utilized as a perfect substrate for the construction of PEC immunosensors, and the SnO2-modified electrode was first coated with CdTe quantum dots (QDs) and then further deposited with CdS by successive ionic layer adsorption and reaction techniques. The formed SnO2/CdS/CdTe-cosensitized structure exhibited excellent photocurrent intensity and was employed as an excellent photoactive matrix to immobilize Aβ antibody to further construct the immunosensor. Under optimal conditions, the as-constructed PEC immunosensor was used to detect Aβ and exhibited a wide linear concentration range from 0.5 pg mL-1 to 10 ng mL-1, with a low limit of detection (LOD, 0.18 pg mL-1, S/N = 3). Meanwhile, it also presented good reproducibility, specificity, and stability and may open a new promising platform for the clinical detection of Aβ or other biomarkers.

The point of fabricating ultrasensitive electrochemiluminescence (ECL)-based biosensors should be focused on how to maintain high immune recognition of antigens by antibodies in whole process. That is not effortless due to the structure of the protein can be destroyed root in toxic nanocarriers, excessive cyclic potential and superoxide radicals in coreactant, all of which can lead to reduce the bioactivity of antigen and antibody. In this work, the effect of negative voltage and divers coreactant on protein bioactivity were verified. Based on that, a motivated ECL biosensor with good biocompatibility was fabricated for procalcitonin (PCT) detection using Au nanoclusters (Au NCs) as low-potential cathodic luminophor and K 2 S 2 O 8 as non-toxic coreactant, respectively. Besides, highly-branched Cu 2 O was utilized to catalyze K 2 S 2 O 8 and produce more radical anion SO 4 •- , which can oxidize Au NCs •- to generate more high-energy-state Au NCs*, thus doubling the ECL intensity to meet the requirements of trace analysis. In addition, protein A (PA) as specific antibody capturer was employed to bind the Fc region of anti-PCT in an orientated way, further maintaining the physiological activity of antibody. As expected, all strategies undoubtedly practically improved the immune recognition of the biosensor and reduced the detection limit to 2.90 fg/mL., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In this work, by using amorphous bimetallic sulfides of CoSnS x Pd as signal amplifier and magnetic material of Fe 3 O 4 @PPyAu as the substrate, we fabricated an electrochemical immunoassay for Nterminal prohormone of brain natriuretic peptide (NTpro BNP). CoSnS x was used as the signal amplifier of the immunosensor for the first time, which was synthesized by fast stoichiometric co-precipitation method. The binary sulfide was identified as an amorphous structure and performed apparent electrochemical behavior. The excellent performance of signal marker was induced by the synergistic effect between SnS 2 and cobalt, as well as the loaded Pd nanoparticles (NPs). Both CoSnS x and Pd NPs presented excellent electrocatalytic activity toward H 2 O 2 oxidation. Moreover, the magnetic nanocomposite of Fe 3 O 4 @PPyAu was firmly immobilized on the magnetic glassy carbon electrode (MGCE) by the magnetic force. The magnetic substrate not only performed good electron conductivity, but also improved the stability of the fabricated electrochemical immunosensor. The developed immunosensor for the NTpro BNP detection exhibited a wide linear response (0.1 pg/mL to 50 ng/mL), and low detection limit of 31.5 fg/mL. In addition, the immunosensor held an excellent analysis capability and broad fascinating application for the detection of other biomarkers in medical diagnosis and treatment., (Copyright © 2019 Elsevier B.V. All rights reserved.)

An ultrasensitive label-free photoelectrochemical (PEC) immunosensor with high visible-light activity was developed for quantitative detection of amyloid β-protein (Aβ) by cross-linking anti-Aβ antibody onto the Ag 2 S sensitized SnO 2 /SnS 2 nanocomposites. Specifically, SnO 2 with flower-like porous nanostructure was innovatively applied in PEC immunosensor as a basal material. It could form a heterostructure with SnS 2 , which brought about the sensitization of SnO 2 and enhanced the separation of photogenerated electrons and holes. Moreover, Ag 2 S was in-situ growth on the surface of SnO 2 /SnS 2 , which further enhanced the photocurrent response significantly. Therefore, SnO 2 /SnS 2 /Ag 2 S could form stepwise band-edge structure, which benefited the light harvesting and provided a good foundation for sensor construction and detection. Under optimal conditions, the PEC immunosensor was used to detect the content of Aβ and exhibited a wide linear concentration range from 0.5 pg mL -1 to 100 ng mL -1 , with low limit of detection (0.17 pg mL -1 ) and limit of quantification (0.56 pg mL -1 ). Additionally, the designed PEC immunosensor exhibited good reproducibility, specificity, and stability which may find potential applications in the biosensor, biomedicine, clinical diagnosis, photocatalysis and other related fields., (Copyright © 2018 Elsevier B.V. All rights reserved.)