Signal-On Detection of Dopamine and Tyrosinase Using Tris(hydroxypropyl)phosphine as a New Lucigenin Chemiluminescence Coreactant.

Dopamine (DA) is a very imperative neurotransmitter in our body, since it contributes to several physiological processes in our body, for example, memory, feeling, cognition, cardiovascular diseases, and hormone secretion. Meanwhile, tyrosinase is a critical biomarker for several dangerous skin diseases, including vitiligo and melanoma cancer. Most of the reported chemiluminescent (CL) methods for monitoring DA and tyrosinase are signal-off biosensors. Herein, we introduce a new chemiluminescent "signal-on" system, lucigenin-tris(hydroxypropyl)phosphine (THPP), for the selective determination of DA and tyrosinase. THPP is well known as a versatile and highly water-soluble sulfhydryl-reducing compound that is more highly stable against air oxidation than common disulfide reductants. By employing THPP for the first time as an efficient lucigenin coreactant, the lucigenin-THPP system has shown a high CL response (approximately 16-fold) compared to the lucigenin-H2O2 classical CL system. Surprisingly, DA can remarkably boost the CL intensity of the lucigenin-THPP CL system. Additionally, tyrosinase can efficiently catalyze the conversion of tyramine to DA. Therefore, lucigenin-THPP was employed as an ultrasensitive and selective signal-on CL system for the quantification of DA, tyrosinase, and THPP. The linear ranges for the quantification of DA, tyrosinase, and THPP were 50-1000 nM, 0.2-50 µg/mL, and 0.1-800 µM, respectively. LODs for DA and tyrosinase were estimated to be 24 nM and 0.18 µg/mL, respectively. Additionally, the CL system has been successfully employed for the detection of tyrosinase in human serum samples and the assay of DA in human serum samples as well as in dopamine injection ampules with excellent obtained recoveries.

Metal-Organic Framework-Derived High-Entropy Oxides as Coreaction Accelerators for an Efficient Luminol/Dissolved Oxygen Electrochemiluminescence System for Ultrasensitive Mercury Detection.

The development of luminol-dissolved O2 (luminol-DO) electrochemiluminescence (ECL) systems is crucial for real-world applications. Despite its stability and low biotoxicity, luminol-DO ECL systems struggle with low ECL performance due to their low reactivity. Investigating new materials like coreactant accelerators increases reactive oxygen species (ROS) formation and enhances luminol-DO ECL intensity. Motivated by the ROS-mediated ECL process, for the first time, we designed oxygen vacancy (OV)-rich high-entropy oxides (HEO) with five metal components [(FeCoNiCuZn)O] derived from metal-organic frameworks (MOFs) as coreaction accelerators to establish efficient luminol-DO ECL systems. High entropy (HE) MOFs were annealed at four different temperatures (600, 700, 800, and 900 °C). Indeed, the HE MOFs annealed at 800 °C (HEO-800) showed a 120-fold stronger ECL intensity compared to the bare glassy carbon electrode in the luminol-DO ECL system. The enhanced ECL performance can be attributed to the porous structure, unique morphology, heterostructures, high-density active sites, rich OV, unsaturated metals, and synergistic impact, which act as catalysts to accelerate the conversion of DO to ROS. The developed HEO-800-based luminol-DO ECL system can be effectively used for the high-sensitivity detection of mercury ions (Hg2+). The system detected Hg2+ over a wide concentration range from 0.1 nM to 100 µM, with a detection limit of 0.02 nM. The sensing mechanism relied on high-affinity metallophilic Hg2+-HEO-800 interactions, effectively quenching the ECL intensity of the luminol-DO/HEO-800 ECL system. The ECL sensing platform, developed without H2O2, offers a novel method for detecting substances, demonstrating significant potential for clinical diagnosis and biomarker analysis.

Remarkably Enhanced Luminol/H2O2 Chemiluminescence with Excellent Peroxidase-like Activity of FeCoNi-based Metal-Organic Xerogels for the Sensitive Detection of Dopamine.

Metal-organic gels (MOGs) are a category of metal-organic smart soft materials with large specific surface areas, loose porous structures, and open metal active sites. In this work, trimetallic Fe(III)Co(II)Ni(II)-based MOGs (FeCoNi-MOGs) were synthesized at room temperature via a simple and mild one-step procedure. Fe3+, Co2+, and Ni2+ were the three central metal ions in it, while 1,3,5-benzenetricarboxylic acid (H3BTC) served as the ligand. The solvent enclosed in it was then removed by freeze-drying to get the corresponding metal-organic xerogels (MOXs). The as-prepared FeCoNi-MOXs have excellent peroxidase-like activity and can significantly enhance luminol/H2O2 chemiluminescence (CL) by more than 3000 times, which is very effective compared with other reported MOXs. Based on the inhibitory effect of dopamine on the CL of the FeCoNi-MOXs/luminol/H2O2 system, a simple, rapid, sensitive, and selective CL method for dopamine detection was established with a linear range of 5-1000 nM and a limit of detection of 2.9 nM (LOD, S/N = 3). Furthermore, it has been effectively used for the quantitative measurement of dopamine in dopamine injections and human serum samples, with a recovery rate of 99.5-109.1%. This research brings up prospects for the application of MOXs with peroxidase-like activity in CL.