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.

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.

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.

Light Scattering and Luminophore Enrichment-Enhanced Electrochemiluminescence by a 2D Porous Ru@SiO2 Nanoparticle Membrane and Its Application in Ultrasensitive Detection of Prostate-Specific Antigen.

Electrochemiluminescence (ECL) by virtue of its controllability and versatility has emerged as a significant tool in bioassay, but how to integrate it with other (nano)materials and further break the limit of sensitivity for ultrasensitive detection still possess tremendous potential. Herein, a close-packed Ru@SiO2 NP nanomembrane that serves as an enhanced substrate and luminophore enricher simultaneously was constructed by the liquid-liquid interface self-assembly method and applied for ECL-enhanced bioassay. The developed ECL electrode obtained ∼600-fold enhancement on ECL intensity compared with the bare ITO electrode and ∼21-fold enhancement compared with the SiO2 NP nanomembrane electrode due to the dramatic light scattering of the 2D SiO2 NPs and the enrichment of Ru(bpy)32+ molecules on the surface of the Ru@SiO2 NP nanomembrane electrode. Based on the fascinating Ru@SiO2 NP nanomembrane platform, we further constructed a label-free immunosensor for the detection of prostate-specific antigen (PSA). The as-fabricated Ru@SiO2-nanomembrane ECL immunosensor exhibited good stability and performed ultrasensitive detection with an utmost low detection limit of 0.169 fg·mL-1 (signal/noise = 3). Our work puts forward an effective solution benefiting for further improving ECL performance for ultrasensitive bioassays.

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.

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.

Highly sensitive and selective non-enzymatic glucose detection based on indigo carmine/hemin/H2O2 chemiluminescence.

A new chemiluminescence (CL) system, indigo carmine/glucose/hemin/H2O2, has been found and developed for non-enzymatic detection of indigo carmine (IC) and glucose. The CL response increases linearly with IC concentrations from 3.2 µM to 10 mM and glucose concentrations from 0.06 µM to 3.5 mM. The detection limits are 1.45 µM and 15.0 nM for IC and glucose, respectively. This method allows the determination of glucose in blood and urine after simple dilution. The recoveries for the determination of glucose are between 98.5% and 101.0% in blood and between 98.5% and 101.3% in urine. This method shows good sensitivity, selectivity, simplicity, and is low cost, suggesting its promising broad applications.

Recent advances in nanomaterial-based capillary electrophoresis.

This review gives a summary of applications of different nanomateials, such as gold nanoparticles (AuNPs), carbon-based nanoparticles, magnetic nanoparticles (MNPs), and nano-sized metal organic frameworks (MOFs), in electrophoretic separations. This review also emphasizes the recent works in which nanoparticles (NPs) are used as pseudostationary phase (PSP) or immobilized on the capillary surface for enhancement of separation in CE, CEC, and microchips electrophoresis.

Determination of Concentrated Hydrogen Peroxide Free from Oxygen Interference at Stainless Steel Electrode.

H2O2 is frequently used at high concentrations in various applications. It is very challenging to detect high concentrations of H2O2 and to eliminate oxygen interference for H2O2 detection through electrochemical reduction. In the present investigation, the electrochemistry of H2O2 at stainless steel electrode has been carried out for the first time. A cathodic peak for H2O2 reduction was observed at about -0.40 V, and no cathodic peak for dissolved oxygen reduction was observed on type 304 stainless steel electrode. Amperometric determination of H2O2 on type 304 stainless steel electrode displayed a linear range from 0.05 up to 733 mM with a detection limit of 0.02 mM (S/N = 3) and a sensitivity of 16.7 µA mM-1 cm-2. The type 304 stainless steel electrode not only shows much higher upper limit than other reported electrodes for the detection of concentrated H2O2 but also is free from oxygen interference, which is of great importance for practical applications. This method could detect H2O2 in wound wash and lake water with excellent recoveries. Moreover, we successfully applied the stainless steel electrode to determine glucose using glucose oxidase to catalyze the oxidation of glucose to generate hydrogen peroxide. The linear range for glucose is between 0.5 and 25 mM, which covers clinically important blood glucose concentrations well.

Tris(2,2'-bipyridyl)ruthenium(II) electrochemiluminescent determination of ethyl formate.

Ethyl formate is extensively used as food flavor, fungicide, and larvicide. It naturally exists in coffee, fruits, honey, brandy, and rum as well as dust clouds in an interstellar space of the Milky Way galaxy. Herein, its electrochemiluminescence (ECL) property has been firstly investigated. It shows intense ECL in reaction with Ru(bpy)32+ as luminophore, and thus a rapid and sensitive detection method for ethyl formate is proposed. Effects of pH, working potential, scan rate, and concentration of Ru(bpy)32+ were studied. ECL spectrum analysis was used to reveal the reaction mechanism. At the optimized experimental conditions, a linear relationship between ECL intensities and concentrations of ethyl formate is observed from 3.0 µM to 1.0 mM (R2 = 0.997). The limit of detection for ethyl formate is 0.7 µM (S/N = 3). The relative standard deviation with 1.0 mM concentration of ethyl formate for nine analyses is 2.7%. A 101.20-102.10% recovery was obtained in a real samples analysis. Graphical Abstract ᅟ.

Chemiluminescence of Lucigenin-Allantoin and Its Application for the Detection of Allantoin.

Allantoin has been reported as a promising biomarker for monitoring of oxidative stress in humans and widely utilized in a variety of topical pharmaceuticals and cosmetics. Currently, the detection of allantoin is achieved by using chromatographic coupled techniques, which needs sample pre-extraction, derivatization, complex matrixes, and expensive instrumentation. Herein we report both the intense chemiluminescence of allantoin with lucigenin and the chemiluminescent detection of allantoin for the first time. The lucigenin-allantoin system demonstrated chemiluminescence emission intensity 17 times higher than that of the classic lucigenin-hydrogen peroxide system. Based on this fascinating phenomenon, a novel chemiluminescence method has been developed for the sensitive and selective allantoin determination with the combination of flow injection analysis. This method shows a linear calibration curve in the range 0.1-3000 µM with a detection limit (3σ/s) of 0.03 µM. Moreover, it was successfully utilized for the determination of allantoin in human eye drop and real urine samples after simple dilution with water. It shows excellent recoveries in the range 94.0-101.7%, and each measurement takes a very short time. This method exhibits potential advantages in the form of simplicity, rapidity, sensitivity, selectivity, and low cost. Allantoin could be an effective candidate for constructing new chemiluminescence systems, and it may provide a broad range of sensing applications.

Stainless Steel Electrode for Sensitive Luminol Electrochemiluminescent Detection of H2O2, Glucose, and Glucose Oxidase Activity.

Electrogenerated chemiluminescence (ECL) application of stainless steel, a robust and cost-effective material, has been developed for the first time. Type 304 stainless steel electrode shows appealing ECL performance in the luminol-H2O2 system. It enables the detection of H2O2 with a linear range from 1 to 1000 nM and a limit of detection of 0.456 nM [signal-to-noise ratio (S/N) = 3]. The ECL method based on type 304 stainless steel electrode is more sensitive, more cost-effective, and much simpler than other ECL methods reported before. Because the stainless steel electrode has excellent performance for H2O2 detection and H2O2 participates in many important enzymatic reactions, applications of stainless steel electrode-based ECL for detection of enzyme activities and enzyme substrates were further investigated by use of glucose oxidase (GODx) and glucose as representative enzyme and substrate. The concentrations of glucose and the activity of GODx were directly proportional to ECL intensities over a range of 0.1-1000 µM and 0.001-0.7 units/mL with limits of detection of 0.076 µM and 0.00087 unit/mL (S/N = 3), respectively. This method was successfully used for determining glucose in honey. Because of their remarkable performance and user-friendly features, stainless steel electrodes hold great promise in various electroanalytical applications, such as biosensing, disposable sensors, and wearable sensors.

Artemisinin-Luminol Chemiluminescence for Forensic Bloodstain Detection Using a Smart Phone as a Detector.

Forensic luminol chemiluminescence test is one of the most sensitive and popular methods for the determination of latent bloodstains. It mainly uses hydrogen peroxide or sodium perborate as coreactants. The easy decomposition of hydrogen peroxide and sodium perborate in the presence of many ions significantly affects the selectivity. Artemisinin is a natural peroxide that is quite stable in the presence of common ions. In the present study, artemisinin has been exploited for the forensic bloodstain chemiluminescence detection for the first time. Using smart phone as cost-effective portable detector, the visual detection of bloodstains has been achieved with a dilution factor of blood up to 100 000. Moreover, this system shows excellent selectivity against many common species. It can well differentiate bloodstains from other stains, such as coffee, brown sugar, and black tea. Both favorable sensitivity and selectivity makes the present method promising in forensic detection.

Ultrasensitive Glutathione Detection Based on Lucigenin Cathodic Electrochemiluminescence in the Presence of MnO2 Nanosheets.

Glutathione (GSH) is a crucial antioxidant produced endogenously and plays key roles in biological systems. It is vitally important to design simple, selective, and sensitive methods to sense GSH and monitor changes of GSH concentration. In this work, the cathodic electrochemiluminescence (ECL) of lucigenin in the presence of MnO2 nanosheets at a glassy carbon electrode was utilized for GSH detection. GSH can reduce MnO2 nanosheets into Mn(2+) which can obviously inhibit the ECL of lucigenin. The ECL inhibition efficiencies increase linearly with the concentrations of glutathione in the range of 10 to 2000 nM. The detection limit for GSH measurement is 3.7 nM. This proposed method is highly sensitive, selective, simple, fast, and cost-effective. Moreover, this approach can detect GSH in human serum samples with excellent recoveries, which indicates its promising application under physiological conditions.

Electrogenerated chemiluminescence of tris(2,2'-bipyridine)ruthenium(II) using N-(3-aminopropyl)diethanolamine as coreactant.

Coreactant plays a critical role for the application of electrochemiluminescence (ECL). Herein, N-(3-aminopropyl)diethanolamine (APDEA) has been explored as a potential coreactant for enhancing tris(2,2'-bipyridyl)ruthenium(II) ECL. It is much more effective than tripropylamine at gold and platinum electrodes although it has one primary amine group besides a tertiary amine group. The presence of primary amine group and hydroxyl groups in APDEA promotes the oxidation rates of amine and thus remarkably increases ECL intensity. The ECL intensities of the Ru(bpy)3 (2+)/APDEA system are approximately 10 and 36 times stronger than that of Ru(bpy)3 (2+)/tripropylamine system and about 1.6 and 1.14 times stronger than that of Ru(bpy)3 (2+)/N-butyldiethanolamine system at Au and Pt electrodes, respectively. The ECL intensity of the Ru(bpy)3 (2+)/APDEA system is 2.42 times stronger than that of Ru(bpy)3 (2+)/N-butyldiethanolamine at glassy carbon electrodes.

Voltammetric determination of tryptophan at graphitic carbon nitride modified carbon paste electrode.

Herein, we reported carbon paste electrode modified with graphitic carbon nitride (g-C3N4-CPE) to determine of tryptophan (Trp) using voltametric techniques. Various spectroscopic and electrochemical techniques were used to characterize the as-synthesized g-C3N4 and the assembled electrodes. The transfer coefficient, rate constant and the diffusion coefficient of Trp in this system were found to be 0.28, 1.9 × 104 M-1s-1 and 3.2 × 10-5 cm2s-1, respectively. The linear range was obtained for the detection of Trp using LSV is from 0.1 µM to 120 µM at pH 5. The limit of detection (LOD) (3σ/m) was 0.085 µM. The demonstrated modified CPE was also effectively used for the detection of Trp in milk with percentage recovery of 98 %-105.2 %. Furthermore, the modified CPE exhibited good repeatability, reproducibility and appropriate selectivity.

Effervescent powder-assisted floating organic solvent-based dispersive liquid-liquid microextraction for determination of organochlorine pesticides in water by GC-MS.

An effervescent powder-assisted floating organic solvent-based dispersive liquid-liquid microextraction was introduced for determination of 13 organochlorine pesticides in water samples. In this method, a less toxic low-density organic solvent was used as extraction solvent. The extraction solvent was dispersed in to the aqueous sample via CO2 bubbles, in-situ generated up on addition of water to a falcon tube containing the mixture of effervescent powder precursors as well as the extraction solvent. Various experimental parameters such as effervescent and its weight fractions, extraction solvent type and its volume, the total mass of effervescent precursors, and the effect of salt were investigated and the optimal conditions were established. Under the optimum conditions, the proposed method exhibited good linearity for all target pesticides with the coefficient of determinations varying from 0.9981 to 0.9997. The limits of detection and quantification were within the range of 0.03-0.24 and 0.26-0.75 µg/L, respectively. The intra- and inter-day precisions which were expressed in terms of the relative standard deviation ranged from 0.33 to 4.47 and 0.51-5.52%, respectively. The enrichment factors and recoveries ranged from 24 to 293 and 76-116%, respectively. The proposed method could be used simple, cheap, fast, and environmentally friendly alternative for analysis of organochlorine pesticides from environmental water and other similar matrices.

Ternary solvent based homogeneous liquid-liquid microextraction for the preconcentration of organochlorine pesticides from water and apple juice samples.

In the present study, the optimal experimental conditions were determined by optimizing the effect of extraction solvent types and volume, salt types and concentration, centrifugation speed and time using one variable at a time. Under optimal experimental conditions, calibration curves were constructed separately using water and apple juice samples as representative matrices, and good linearities were achieved over a wide concentration range of 0.2-1600 ng L-1 with a coefficient of determination (r2) ≥ 0.998. The limits of detection (LOD) and limits of quantification (LOQ), determined to be 3 and 10 times the signal-to-noise ratios (S/N), were between 0.07-3.9 and 0.2-12.0 ng L-1 for water samples and 2.6-10.0 and 8.0-30.0 ng L-1 for the apple juice sample respectively. The precisions study showed %RSD values of ≤6% for both matrices, indicating satisfactory precisions. The enrichment factors and recoveries of the proposed method ranged from 41.4-74.5 and 86-109% respectively. The proposed method could be used as a simple and environmentally friendly alternative for the analysis of OCPs from environmental and food matrices. This method potentially offers a more sustainable and effective approach to monitoring OCPs in environmental and food products. Its use in the analysis of apple juice samples is particularly novel and can provide valuable insights into pesticide contamination in fruit juices.

Nitrogen Defect-Rich Graphitic Carbon Nitride for Highly Sensitive Voltammetric Determination of Tryptophan.

Here, a highly sensitive electrochemical sensor for detection of tryptophan (Trp) using a nitrogen defect graphitic carbon nitride-modified glassy carbon electrode (ND-CN/GCE) was introduced. ND-CN/GCE showed a higher oxidation current for Trp than the graphitic carbon nitride-modified glassy carbon electrode (g-CN/GCE) and bare glassy carbon electrode (BGCE). The synthesized nitrogen defect-rich graphitic carbon nitride (ND-CN) was characterized using X-ray photoelectron spectroscopy, X-ray diffraction spectroscopy, Fourier-transform infrared spectroscopy, scanning electron microscopy, and transmission electron microscopy. Electrochemical impedance spectroscopy and cyclic voltammetry were used to further analyze the electrochemical properties of BGCE, g-CN/GCE, and ND-CN/GCE. The oxidation of Trp at ND-CN/GCE is a diffusion-controlled process at pH 3.0. It was calculated that the transfer coefficient, rate constant, and diffusion coefficient of Trp were 0.53, 2.24 × 103 M-1 s-1, and 8.3 × 10-3 cm2 s-1, respectively, at ND-CN/GCE. Trp was detected using square wave voltammetry, which had a linear range from 0.01 to 40 µM at pH 3.0 and a limit of detection of about 0.0034 µM (3σ/m). Analyzing the presence of Trp in a milk and multivitamin tablet sample with a percentage recovery in the range of 97.0-108% satisfactorily demonstrated the practical usability of the electrochemical sensor. The ND-CN/GCE additionally displays good repeatability and reproducibility and satisfactory selectivity.

Gold nanoparticle-based signal amplified electrochemiluminescence for biosensing applications.

Since the content levels of biomarkers at the early stage of many diseases are generally lower than the detection threshold concentration, achieving ultrasensitive and accurate detection of these biomarkers is still one of the major goals in bio-analysis. To achieve ultrasensitive and reliable bioassay, it requires developing highly sensitive biosensors. Among all kinds of biosensors, electrogenerated chemiluminescence (ECL) based biosensors have attracted enormous attention due to their excellent properties. In order to improve the performance of ECL biosensors, gold nanoparticles (Au NPs) have been widely utilized as signal amplification tags. The introduction of Au NPs could dramatically enhance the performance of the constructed ECL biosensors via diverse ways such as electrode modification material, efficient energy acceptor in ECL resonant energy transfer (ECL-RET), reaction catalyst, surface plasmon resonance (SPR) enhancer, and as nanocarrier. Herein, we summarize recent developments and progress of ECL biosensors based on Au NPs signal amplification strategies. We will cover ECL applications of Au NPs as a signal amplification tag in the detection of proteins, metal ions, nucleic acids, small molecules, living cells, exosomes, and cell imaging. Finally, brief summary and future outlooks of this field will be presented.