Boosting Electrochemiluminescence Performance of a Dual-Active Site Iron Single-Atom Catalyst-Based Luminol-Dissolved Oxygen System via Plasmon-Induced Hot Holes.

Due to the commonly low content of biomarkers in diseases, increasing the sensitivity of electrochemiluminescence (ECL) systems is of great significance for in vitro ECL diagnosis and biodetection. Although dissolved O2 (DO) has recently been considered superior to H2O2 as a coreactant in the most widely used luminol ECL systems owing to its improved stability and less biotoxicity, it still has unsatisfactory ECL performance because of its ultralow reactivity. In this study, an effective plasmonic luminol-DO ECL system has been developed by complexing luminol-capped Ag nanoparticles (AgNPs) with plasma-treated Fe single-atom catalysts (Fe-SACs) embedded in graphitic carbon nitride (g-CN) (pFe-g-CN). Under optimal conditions, the performance of the resulting ECL system could be markedly increased up to 1300-fold compared to the traditional luminol-DO system. Further investigations revealed that duple binding sites of pFe-g-CN and plasmonically induced hot holes that disseminated from AgNPs to g-CN surfaces lead to facilitate significantly the luminous reaction process of the system. The proposed luminol-DO ECL system was further employed for the stable and ultrasensitive detection of prostate-specific antigen in a wide linear range of 1.0 fg/mL to 1 µg/mL, with a pretty low limit of detection of 0.183 fg/mL.

Ultrafast Response and High Selectivity of Diethylamine Gas Sensors at Room Temperature Using MOF-Derived 1D CuO Nano-Ellipsoids.

Environmental and health monitoring requires low-cost, high-performance diethylamine (DEA) sensors. Materials based on metal-organic frameworks (MOFs) can detect hazardous gases due to their large specific surface area, many metal sites, unsaturated sites, functional connectivity, and easy calcination to remove the scaffold. However, developing facile materials with high sensitivity and selectivity in harsh environments for accurate DEA detection at a low detection limit (LOD) at room temperature (RT) is challenging. In this study, p-type semiconducting porous CuOx sensing materials were synthesized using a simple solvothermal process and annealed in an argon atmosphere at three different temperatures (x = 400, 600, and 800 °C). Significant variations in particle size, specific area, crystallite size, and shape were noticed when the annealing temperature was elevated. Cu-MIL-53 annealed at 400 °C (CuO-400) has a typical nanoellipsoid (NEs) shape with a length of 61.5 nm and a diameter of 33.2 nm. Surprisingly, CuO-400 NEs showed an excellent response to DEA with an ultra-LOD (Rg/Ra = 7.3 @ 100 ppb, 55% relative humidity), excellent selectivity and sensitivity (Rg/Ra = 236 @ 15 ppm), exceptional long-term stability and repeatability, and a fast response/recovery period at RT, outperforming most previously reported materials. CuO-400 NEs have outstanding gas-sensing characteristics due to their high porosity, 1D nanostructure, unsaturated Cu sites (Cu+ and Cu2+), large specific surface area, and numerous oxygen vacancies. This study presents a generic approach to produce future CuO derived from Cu-MOFs-sensitive materials, revealing new insights into the design of effective sensors for environmental monitoring at RT.

Tannic Acid-Functionalized Silver Nanoparticles as Colorimetric Probe for the Simultaneous and Sensitive Detection of Aluminum(III) and Fluoride Ions.

In this study, we employed tannic acid (TA)-functionalized silver nanoparticles (TA@AgNPs) as colorimetric probe for the simultaneous and sensitive detection of Al(III) and F- ions. The proposed sensor was based on the aggregation and anti-aggregation effects of target Al(III) and F- ions on TA@AgNPs, respectively. Because of the strong coordination bond between Al(III) ions and TA, the addition of Al(III) ions to TA@AgNPs could cause aggregation and, hence, result in a significant change in the absorption and color of the test solution. Interestingly, in the presence of F- ions, the aggregation effect of Al(III) ions on TA@AgNPs can be effectively prevented. The extent of aggregation and anti-aggregation effects was concentration-dependent and can be used for the quantitative detection of Al(III) and F- ions. The as-proposed sensor presented the sensitive detection of Al(III) and F ions with limits of detection (LOD) of 0.2 and 0.19 µM, respectively. In addition, the proposed sensor showed excellent applicability for the detection of Al(III) and F- ions in real water samples. Moreover, the sensing strategy offered a simple, rapid, and sensitive detection procedure and could be used as a potential alternative to conventional methods, which usually involve sophisticated instruments, complicated processes, and a long detection time.

Generation of Oxygen Vacancies in Metal-Organic Framework-Derived One-Dimensional Ni0.4Fe2.6O4 Nanorice Heterojunctions for ppb-Level Diethylamine Gas Sensing.

Metal-organic frameworks (MOFs) are ideal sensing materials due to their distinctive morphologies, high surface area, and simple calcination to remove sacrificial MOF scaffolds. Oxygen vacancies (Ovs) can be efficiently generated by the thermal annealing of metal oxides in an inert atmosphere. Herein, MIL-53-based Fe and Fe/Ni-MOFs nanorices (NRs) were first prepared by using a solvothermal method, and then one-dimensional (1D) Fe2O3 and Ni0.4Fe2.6O4 NRs were derived from the MOFs after calcination at 350 °C in an air and argon (Ar) atmosphere, respectively. It was found that Ar-annealed Ni0.4Fe2.6O4 NRs have higher Ovs concentrations (82.11%) and smaller NRs (24.3 nm) than air-annealed NRs (65.68% & 31.5 nm). Beneficially, among the synthesized NRs, the Ar-Ni0.4Fe2.6O4 NRs show a higher sensitivity to diethylamine (DEA) (Ra/Rg = 23 @ 5 ppm, 175 °C), low detection limit (Ra/Rg = 1.2 @ 200 ppb), wide dynamic response (Ra/Rg = 93.5@ 30 ppm), high stability (30 days), and faster response/recovery time (4 s/38 s). Moreover, the 1D nanostructure containing heterostructures offers excellent sensing selectivity and a wide detection range from 200 ppb to 30 ppm in the presence of DEA. The outstanding gas sensing behavior can be attributable to synergistic impact, structural advantages, high concentration of Ovs, and the heterojunction interface, which can have profound effects on gas sensor performance. This study provides a unique technique for constructing high-performance gas sensors for ppb-level DEA detection and the formation of Ovs in metal oxides without the need for any additives.

Oxygen Vacancies Induced by Pd Doping in Ni-P2O5/MoO3 Hollow Polyhedral Heterostructures for Highly Efficient Diethylamine Gas Sensing.

Semiconductor metal-oxide materials have a high surface-to-volume ratio and many active sites, making them potentially useful for gas sensing. Dopants introduced into the lattice can improve the catalytic activity of oxides and promote the formation of oxygen vacancies, hence improving the sensing performance of the materials. However, the simple preparation of materials with high sensitivity, selectivity, and a low detection limit remains a challenge. Herein, we report on the synthesis of Ni-P2O5/MoO3 and Pd-doped Ni-P2O5/MoO3 hollow polyhedral heterostructures (HPHSs) and their application in diethylamine (DEA) sensing for the first time. The Pd-doped Ni-P2O5/MoO3 HPHS was synthesized by doping different proportions of palladium-containing precursors using hydrothermal and solid-state reaction techniques. The concentration of oxygen vacancies in the HPHS composite increased by increasing Pd doping from 2 to 6 weight percent (wt %) but later reduced, according to X-ray photoelectron spectroscopy (XPS) measurements. Pd6%Ni-P2O5/MoO3 has the highest sensitivity to DEA (Ra/Rg = 42.5) and is 5.0 times and 42.5 times more sensitive than the pure Ni-P2O5/MoO3 HPHS (Ra/Rg = 8.5) and commercial ammonium phosphomolybdate (Ra/Rg = 1) at 175 °C toward 10 ppm DEA. Moreover, the DEA sensor exhibits a low detection limit (Ra/Rg = 3.5@1 ppm) with a wide dynamic response (Ra/Rg = 145.5@50 ppm). The remarkable improvement in DEA sensitivity is attributed to the hollow polyhedral structure, heterostructures, and oxygen vacancies formed by Pd doping. This study confirms that developing Pd-doped Ni-P2O5/MoO3 HPHSs provides an innovative approach for DEA sensors.

Plasmon-Boosted Fe, Co Dual Single-Atom Catalysts for Ultrasensitive Luminol-Dissolved O2 Electrochemiluminescence Detection of Prostate-Specific Antigen.

Improving the sensitivity of electrochemiluminescence (ECL) systems is highly desired for in vitro ECL diagnosis and bio-detections due to the often-low content of biomarkers in diseases. And dissolved O2 (DO) as a co-reactant is considered superior to H2O2 in the most commonly used luminol ECL systems due to better stability and low biotoxicity, but it still suffers from low ECL performance due to the low reactivity of DO. In this study, an efficient luminol-DO ECL system was developed through the complexing of Fe, Co dual single-atom catalysts (D-SACs) supported by N-doped graphene with the luminol-capped Ag nanoparticles (AgNPs). Benefiting from the electronic interaction between Fe and Co metal sites in the relevant D-SACs and plasmon enhancement of AgNPs, the performance of the corresponding ECL system could be significantly boosted up to ≈677-fold under optimal testing conditions, comparable to the classic luminol-O2 system. Furthermore, the developed luminol-DO ECL system was successfully applied for the stable ultrasensitive detection of prostate-specific antigen (PSA) in a wide linear range of 1 fg/mL to 1 µg/mL, with a low limit of detection (0.98 fg/mL).

High-Entropy Oxide for Highly Efficient Luminol-Dissolved Oxygen Electrochemiluminescence and Biosensing Applications.

The luminol-dissolved O2 (DO) electrochemiluminescence (ECL) sensing system has recently gained growing interest; however, the drawback of the ultra-low ECL signal response greatly hinders its potential quantitative applications. In this work, for the first time, we explored the use of high entropy oxide (HEO) comprising five metal ingredients (Ni, Co, Cr, Cu, and Fe), to accelerate the reduction reaction of DO into reactive oxygen species (ROS) for boosting the ECL performance of the luminol-DO system. Benefiting from the existing abundant oxygen vacancies induced by the unique crystal structure of the HEO, DO could be efficiently converted into ROS, thus significantly boosting the performance of the corresponding ECL sensor (with an ∼240-fold signal enhancement in this study). As a proof of concept, under optimal conditions, the developed HEO-involved luminol-DO ECL sensing system was successfully applied for efficient biosensing of dopamine and alkaline phosphatase with a fine linear range from 1 pM to 10 nM and from 0.01 to 100 U/L as well as a low limit of detection of 5.2 pM and 0.008 U/L, respectively.

Surface-Bonding-Enhanced Self-Co-Reactant Electrogenerated Chemiluminescence for Sensitive and Selective Detection of Thioglycolic Acid in Cosmetics.

Thioglycolic acid (TGA) is an organic compound widely used in cosmetics that cause a variety of health problems when overexposed to it. So far many attempts have been made to develop methods for TGA detection, but most of them need sophisticated instrumentations and are a little bit complicated. Therefore, a simple, cheap and sensitive detection method of TGA is highly desired. Herein, we demonstrated for the first time an Au-S bonding amplified, highly sensitive electrochemiluminescence (ECL) sensing method for TGA detection using tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)3 2+ ) as a luminophore and TGA as a self-co-reactant, via an anodic reaction at the Au electrode surface. Due to different molecular coordination environments of the TGA at the electrode surface, the ECL signal intensity of the developed ECL system gives much higher ECL signal in borate buffer than phosphate buffer of the same pH. Under the optimized experimental conditions, the ECL intensity has a direct relationship with the concentration of TGA in the range of 0.03 µM to 300 µM and a limit of detection of 0.013 µM (3σ/m). The reported ECL system has further been applied for the detection of TGA in cosmetics with acceptable recoveries.

Plasmon-Enhanced Nitrogen Vacancy-Rich Carbon Nitride Electrochemiluminescence Aptasensor for Highly Sensitive Detection of miRNA.

The development of biosensors for biologically important substances with ultralow content such as microRNA is of great significance. Herein, a novel surface plasmon-enhanced electrogenerated chemiluminescence-based aptasensor was developed for ultrasensitive sensing of microRNA by using nitrogen vacancy-rich carbon nitride nanosheets as effective luminophores and gold nanoparticles as plasmonic sources. The introduction of nitrogen vacancies improved the electrochemiluminescence behavior due to improved conductance and electrogenerated chemiluminescence activity. The introduction of plasmonic gold nanoparticles increased the electrochemiluminescence signal intensity by more than eightfold. The developed surface plasmon-enhanced electrogenerated chemiluminescence aptasensor exhibited good selectivity, ultrasensitivity, excellent stability, and reproducibility for the determination of microRNA-133a, with a dynamic linear range of 1 aM to 100 pM and a limit of detection about 0.87 aM. Moreover, the surface plasmon-enhanced electrogenerated chemiluminescence sensor obtained a good recovery when detecting the content of microRNA in actual serum.

Plasmon-Boosted Cu-Doped TiO2 Oxygen Vacancy-Rich Luminol Electrochemiluminescence for Highly Sensitive Detection of Alkaline Phosphatase.

In this study, an effective oxygen vacancy (Ov)-involved luminol-dissolved oxygen (O2) electrochemiluminescence (luminol-DO ECL) system was developed and exploited for ECL sensing applications through significant plasmon enhancement of the Ov-involved weak luminol-DO ECL signals by the combined use of Cu-doped TiO2 oxygen vacancy and a Au@SiO2 nanomembrane. The results disclosed that the ECL response of the corresponding system could be synergistically boosted, and the plausible underlying mechanism has been discussed. Furthermore, for the first time, the developed system has been successfully applied for the highly sensitive detection of alkaline phosphatase with a low limit of detection of 0.005 U/L, with an excellent linear range from 0.005 to 10 U/L, as well as good stability and reproducibility.

Two-Dimensional-Plasmon-Boosted Iron Single-Atom Electrochemiluminescence for the Ultrasensitive Detection of Dopamine, Hemin, and Mercury.

Single-atom catalysts (SACs) have recently been exploited for luminol-dissolved oxygen electrochemiluminescence (ECL); however, they still suffer from low sensitivity and narrow detection range for a real sample assay. In this work, we boost markedly the ECL response of the iron SAC (Fe-SAC)-based system, for the first time, by the excitation of two-dimensional plasmons derived from the Au@SiO2 nanomembrane. The plausible mechanism of plasmon enhancement in the Fe-SAC ECL system has been discussed. The constructed Fe-SAC ECL system has been applied for the ECL detection of dopamine, hemin, and mercury (Hg2+), with pretty low limits of detection of 0.1, 0.7, and 0.13 nM and wider linear ranges of 0.001-1.0, 0.001-10, and 0.01-0.5 nM, respectively, under optimal conditions.

Electrochemiluminescence of Ru(bpy)32+/thioacetamide and its application for the sensitive determination of hepatotoxic thioacetamide.

Thioacetamide (TAA) is a well-known hepatotoxic substance, so it is important to determine its presence and content in food and environmental samples. Herein, we report a highly sensitive determination method for TAA based on the electrochemiluminescence (ECL) of tris(2,2'-bipyridyl)ruthenium(ii) (Ru(bpy)32+) for the first time by using TAA as a new coreactant for Ru(bpy)32+ ECL via an anodic route. The developed Ru(bpy)32+-TAA ECL system allows the determination of TAA with a good dynamic linear range and low limit of detection (LOD) of 0.1 µM to 1000 µM and 0.035 µM (3σ/m), respectively. In addition, the established ECL system can be applied to detect TAA in fruit juice and waste water samples with outstanding recoveries.