Two in One: A Dinuclear Ru(II) Complex for Deep-Red Light-Emitting Electrochemical Cells and as an Electrochemiluminescence Probe for Organophosphorus Pesticides.

The emissive properties of two Ru(II) complexes, [Ru(dmbipy)2L1][PF6]2 (1) and [Ru2(dmbipy)4L2][PF6]4 (2), (where L1 and L2 are π-extended phenanthroline-based ligands and dmbipy = 4,4'-dimethyl-2,2'-bipyridine) have been explored for dual applications, namely, deep-red light-emitting electrochemical cells (LECs) and electrochemiluminescence (ECL) sensors for the detection of organophosphorus pesticides (OPs) that include chlorpyrifos (CPS). A simple single-layer deep-red LEC device comprising 2 is reported that outperforms both its mononuclear derivative 1 and all previously reported dinuclear LECs, with a maximum brightness of 524 cd/m2, an external quantum efficiency of 0.62%, and a turn-on voltage of 3.2 V. Optoelectronic studies reveal that the ECL response of 2 is improved when compared to its mononuclear counterpart 1 and benchmark [Ru(bipy)3]2+ (3). Modified glassy carbon electrodes coated with 2 are highly sensitive deep-red ECL sensors that facilitate the detection of CPS directly from river water and fruit samples without any complex pretreatment steps, operating over a broad logarithmic concentration range, with a low detection limit.

An ultra-sensitive electrochemiluminescence probe based on ternary nanocomposite and boron nitride quantum dots for detection of diazinon.

A new enzyme-free electrochemiluminescence (ECL) pesticide sensor was fabricated based on ternary nanocomposite of ruthenium nanoparticles/silver nanoparticles/graphene oxide on the surface of glassy carbon electrode for ultratrace determination of diazinon. Due to some drawbacks of enzyme-based sensors such as enzyme instability at elevated temperature, humidity, changes of pH, and high price of the enzyme, the use of enzyme was omitted in the construction of the developed sensor. The silver nanoparticles with good electrocatalytic proficiency as a signal improving agent and tris(2,2bipyridine) ruthenium(II) as a popular luminophore were uniformly deposited on the surface of the prepared graphene oxide/GC electrode at nanoscale. Boron nitride quantum dots as an efficient co-reactant created the superior efficiency in amplifying the ECL intensity of the ruthenium-based ECL system. The prepared electrode was utilized for the detection of diazinon via the robust ECL method. For the present sensor, a wide linear dynamic range and low detection limit were achieved (3.0 × 10-15 to 6.5 × 10-9 M and 9.5 × 10-16 M, respectively). The obtained results confirmed the fabrication of the robust ECL probe, which is characterized by the cooperative effect of silver nanoparticles and the attached luminophore species. The main advantage of the presented sensor was that the samples could be diluted so that the effect of the interference species was negligible. Due to excellent properties toward accurate determination of diazinon, the ECL sensor as a new practical platform was applied for quantitative detection of diazinon in some real samples.

Single-step microwave synthesis of a novel ternary nanocomposite as an efficient luminophore and boron nitride quantum dots as a new coreactant for a cathodic ECL monitoring of chlorpyrifos.

In this study, a novel and innovative enzyme-free electrochemiluminescence (ECL) pesticide probe based on a ternary nanocomposite, CuS/CQDs/g-C3N4NS, was demonstrated for the accurate monitoring of chlorpyrifos. Boron nitride quantum dots were introduced as a new and effective coreactant in comparison with other coreactants, such as hydrogen peroxide, peroxydisulfate, and tripropylamine, in the negative potential range for the first time. The nanocomposite as a promoted luminophore was synthesized by a one-pot microwave route. Carbon quantum dots and copper sulfide nanostructures were truly incorporated on the porous graphitized carbon nitride, which displayed a good cooperative effect on the signal improvement. CuS as a co-reaction accelerator and CQDs with a superior luminescence effect produced more radical species, and thus, the ECL signal was amplified. Upon increasing the appropriate concentration of this coreactant in electrolyte media, the signal intensity of the nanocomposite increases. A low detection limit of 3.0 × 10-16 M and a wide range from 2.0 × 10-15 to 7.0 × 10-9 M were gained. Also, the fabricated pesticide sensor presented excellent repeatability for 20 consecutive optical signals, with a RSD of about 1.4%. Owing to its high proficiency, the developed sensor was applied as a new probe for chlorpyrifos analysis in water and fruit samples.

An enzyme-free electrochemiluminescence sensing probe based on ternary nanocomposite for ultrasensitive determination of chlorpyrifos.

Herein, an innovative enzyme free electrochemiluminescence chlorpyrifos sensor was reported based on the incorporation of ternary nanocomposite (ruthenium nanobeads/silver nanoparticles/graphene oxide) on the surface of glassy carbon electrode. The silver nanoparticles as a robust signal enhancing agent were well deposited on the modified graphene oxide/glassy carbon electrode and exhibited supreme electrocatalytic proficiency. Then, Ru(bipy)32+ species in bead-like nanoparticles were uniformly anchored on the surface of the modified electrode with the help of chitosan, as a good crosslinking agent. Boron nitride quantum dots as a new coreactant species showed the excellent proficiency for signal enhancement of the fabricated electrode. The fabricated electrode was successfully used as an ultra-sensitive sensor for trace analysis of chlorpyrifos by ECL technique. The wide linear range and the low detection limit were obtained from 5.0 × 10-15 to 4.2 × 10-9 M and 6.5 × 10-16 M, respectively.

An enzyme-free electrochemiluminescence insulin probe based on the regular attachment of ZnO nanoparticles on a 3-D nickel foam and H2O2 as an efficient co-reactant.

In this study, a highly sensitive, fast, and enzyme-free electrochemiluminescence (ECL) probe based on the decoration of zinc oxide nanoparticles on nickel foam is proposed for insulin determination. A silica film was employed as a size adjusting agent for the modification of the nickel foam surface with ZnO nanoparticles (ZnO NPs). The ECL of the ZnO NP/Ni foam was investigated in a natural medium in the presence of hydrogen peroxide (H2O2) as an efficient co-reactant. With increasing insulin concentration, a remarkable improvement in ECL signal was observed, which proved the enhancing effect of insulin on the ECL emission. The characterization of the ZnO-NP/Ni-foam electrode was performed via electrochemical impedance spectroscopy, Brunauer-Emmett-Teller (BET) surface area measurement, X-ray diffraction, field emission scanning electron microscopy (FESEM), and energy-dispersive X-ray analysis techniques. The fabricated electrode was applied for the trace analysis of insulin using the ultrasensitive ECL method in a phosphate buffer solution. Under the optimal conditions, the results showed excellent performance during insulin determination with a wide linear range of 3.57 × 10-15 M to 2.94 × 10-9 M, a low detection limit of 1.00 × 10-16 M, and a relative standard deviation of 1.03%. The proposed ECL sensor with excellent reproducibility, long-term stability, and high selectivity was used for insulin determination in real serum samples with acceptable outcomes.