VS4 Nanodendrites with Narrow Bandgaps in Activating Dissolved Oxygen for Boosted Chemiluminescence and Hemin Detection by Unexpected Quenching.

Chemiluminescence (CL)-based analytical methods utilize luminophores that need to be activated with an oxidizing agent to trigger CL emission. Despite its susceptibility to decomposition when exposed to external light or trace metals, hydrogen peroxide (H2O2) has been widely used to develop chemiluminescent methods due to the limited number of suitable alternatives for activating chemiluminescent luminophores. Also, analytical methods based on the well-known luminol/H2O2 CL system have low sensitivity. Dissolved oxygen (DO) is a naturally abundant and environmentally benign alternative oxidant for luminol and other CL luminophores. However, DO alone is inactive and needs an efficient catalyst or a coreaction accelerator for its activation. Because of the narrow bandgap of VS4 (ca. 1.12 eV), it can facilitate fast electron-transfer kinetics with an acceptor molecule such as DO. Here, we introduce vanadium tetrasulfide (VS4) to boost CL for the first time. Under the optimized conditions, VS4 nanodendrite catalyzes the generation of reactive oxygen species by activating DO which subsequently reacts with luminol to generate intense CL. It enhances the CL intensity of luminol/DO by about 10,000 times. Surprisingly, hemin remarkably quenches the generated CL of luminol/DO/VS4 nanodendrites, which is completely opposite to its typical enhancement of luminol CL. Based on the remarkable concentration-dependent quenching of the luminol/DO/VS4 nanodendrite CL by hemin, we have developed a sensitive CL method that can selectively detect hemin in the linear concentration range of 1-250 nM and achieved a limit of detection of 0.11 nM. The practical utility of the developed method was demonstrated by the determination of hemin in a pharmaceutical drug for the treatment of acute intermittent porphyria and in human serum. This study demonstrates that VS4 holds great promise in analytical method development.

Recent advances in microchip electrophoresis for analysis of pathogenic bacteria and viruses.

Life-threatening diseases, such as hepatitis B, pneumonia, tuberculosis, and COVID-19, are widespread due to pathogenic bacteria and viruses. Therefore, the development of highly sensitive, rapid, portable, cost-effective, and selective methods for the analysis of such microorganisms is a great challenge. Microchip electrophoresis (ME) has been widely used in recent years for the analysis of bacterial and viral pathogens in biological and environmental samples owing to its portability, simplicity, cost-effectiveness, and rapid analysis. However, microbial enrichment and purification are critical steps for accurate and sensitive analysis of pathogenic bacteria and viruses in complex matrices. Therefore, we first discussed the advances in the sample preparation technologies associated with the accurate analysis of such microorganisms, especially the on-chip microfluidic-based sample preparations such as dielectrophoresis and microfluidic membrane filtration. Thereafter, we focused on the recent advances in the lab-on-a-chip electrophoretic analysis of pathogenic bacteria and viruses in different complex matrices. As the microbial analysis is mainly based on the analysis of nucleic acid of the microorganism, the integration of nucleic acid-based amplification techniques such as polymerase chain reaction (PCR), quantitative PCR, and multiplex PCR with ME will result in an accurate and sensitive analysis of microbial pathogens. Such analyses are very important for the point-of-care diagnosis of various infectious diseases.

Regenerable sensor based on tris(4,7'-diphenyl-1,10-phenanthroline)ruthenium (II) for anodic and cathodic electrochemiluminescence applications.

Tris(4,7'-diphenyl-1,10-phenanthroline) ruthenium (II) dichloride [Ru(dpp)32+] was used for the first time to construct a regenerable electrochemiluminescence (ECL) sensor. The Ru(dpp)32+-modified carbon paste electrode (CPE) showed several unique features in comparison with commonly studied Ru(bpy)32+-modified electrodes. On the one hand, a quite reversible reduction peak was observed at -0.96 V where no obvious hydrogen evolution occured, enabling the sensitive detection of S2O82-. Moreover, our proposed S2O82- sensor showed a good linear range from 3 × 10-9 to 3 × 10-4 M with a detection limit of 2 nM, indicating higher sensitivity for the same analyte than previously reported ECL methods by about two orders of magnitude. On the other hand, the Ru(dpp)32+-modified electrode showed an irreversible oxidation peak because electrogenerated Ru(dpp)33+ is very reactive in aqueous solutions, while Ru(bpy)32+-modified electrode showed a reversible oxidation peak. Moreover, the present sensor showed a good linear range from 10-7 M to 10-3 M for oxalate with a detection limit of 60 nM. It detected oxalate in urine samples with nice recoveries. The regenerable ECL sensor presented good characteristics, such as low cost, simple fabrication procedure and fast response time. The Ru(dpp)32+ based regenerable sensor is an attractive alternative to Ru(bpy)32+-based regenerable sensor, as it can be used for both anodic and cathodic ECL analysis with high sensitivity in aqueous media.

Hard Carbons as Anodes in Sodium-Ion Batteries: Sodium Storage Mechanism and Optimization Strategies.

Sodium-ion batteries (SIBs) are regarded as promising alternatives to lithium-ion batteries (LIBs) in the field of energy, especially in large-scale energy storage systems. Tremendous effort has been put into the electrode research of SIBs, and hard carbon (HC) stands out among the anode materials due to its advantages in cost, resource, industrial processes, and safety. However, different from the application of graphite in LIBs, HC, as a disordered carbon material, leaves more to be completely comprehended about its sodium storage mechanism, and there is still plenty of room for improvement in its capacity, rate performance and cycling performance. This paper reviews the research reports on HC materials in recent years, especially the research process of the sodium storage mechanism and the modification and optimization of HC materials. Finally, the review summarizes the sterling achievements and the challenges on the basis of recent progress, as well as the prospects on the development of HC anode materials in SIBs.

The role of doping strategy in nanoparticle-based electrochemiluminescence biosensing.

Doping plays a crucial role in electrochemiluminescence (ECL) due to the followings: (1) Modulation of electronic structure, alteration of the surface state of nanoparticles (NPs), providing effective protection from the surrounding environment, thereby leading to ECL emitters with exceptional properties including tunable spectra, high luminescence efficiency, low excitation potential, and good stability. (2) Employment of doped NPs as promising coreactant alternatives due to the presence of functional groups such as amines induced by NP doping. (3) Serving as novel co-reaction accelerators (CRAs) for ECL through doping induced high catalytic properties. (4) Behaving as excellent carriers to load ECL emitters, recognition elements, and catalysts due to doping-induced larger surface area, higher conductivity and better biocompatibility of NPs. As a consequence, doped NPs have aroused broad interest and found wide applications in various ECL sensing platforms. In this review, the current promising improvements, concepts, and excellent applications of doped NPs for ECL biosensing are addressed. We aim to bring to light the physicochemical characteristics of various doped NPs that endow them with appealing ECL performance, leading to diverse applications in biosensing.

Dithiothreitol-Lucigenin Chemiluminescent System for Ultrasensitive Dithiothreitol and Superoxide Dismutase Detection.

1,4-Dithiothreitol (DTT), a highly water-soluble and well-known reducing agent for preservation and regeneration of sulfhydryl groups in biomedical applications, has been developed as an efficient and stable coreactant of lucigenin for the first time. DTT efficiently reacts with lucigenin to generate intense chemiluminescence (CL), eliminating the need for external catalysts to facilitate the lucigenin CL. The DTT-lucigenin CL is approximately 15-fold more intense when compared with the lucigenin-H2O2 classical system. Superoxide dismutase (SOD) remarkably quenches the DTT-lucigenin CL. Based on this phenomenon, a newly developed CL approach for the determination of SOD was proposed with a linear range of 0.01-1.5 µg/mL and a limit of detection of 2.2 ng/mL. Various factors affecting the CL emission of the DTT-lucigenin probe were studied and optimized. Plausible mechanistic pathways for the CL coreaction of lucigenin with DTT were proposed and fully discussed. Our proposed method not only has the merit of being selective toward the target analytes but also eliminates the need for the complex synthesis of luminescent probes and facilitates the sensitive detection of SOD in human serum and cosmetics SOD raw material with satisfactory recoveries.

Recent advances in electrochemiluminescence luminophores.

Electrochemiluminescence (ECL) has continued to receive considerable attention in various applications, owing to its intrinsic advantages such as near-zero background response, wide dynamic range, high sensitivity, simple instrumentation, and low cost. The ECL luminophore is one of the most significant components during the light generation processes. Despite significant progress that has been made in the synthesis of new luminophores and their roles in resolving various challenges, there are few comprehensive summaries on ECL luminophores. In this review, we discuss some of the recent advances in organic, metal complexes, nanomaterials, metal oxides, and near-infrared ECL luminophores. We also emphasize their roles in tackling various challenges with illustrative examples that have been reported in the last few years. Finally, perspective and some unresolved challenges in ECL that can potentially be addressed by introducing new luminophores have also been discussed. Graphical abstract.

Sonochemiluminescence Using Apertureless USB Piezoelectric Ultrasonic Transducer and Its Applications for the Detection of Hydrogen Peroxide, Glucose, and Glucose Oxidase Activity.

The mesh-type USB piezoelectric ultrasonic transducer (USB-PUT) used in household humidifiers and inhalation therapy devices is very cheap, small, and energy saving. It holds great promise for sonochemistry. However, the microtapered apertures in the center of the stainless steel substrate of mesh-type USB-PUT can lead to rapid atomization of solution, leakage of solutions containing surfactants and organic solvent through the apertures, and high background emission. Herein, we design a new type of USB-PUT by replacing the meshed stainless steel substrate with an apertureless stainless steel substrate. We have found that this apertureless USB-PUT can not only induce intense sonochemiluminescence (SCL) but can also enable sensitive luminol SCL detection of hydrogen peroxide which is practically impossible using mesh-type PUT because of the strong background SCL emission. By using this apertureless device to induce SCL and using smart phone as a detector, a visual hydrogen peroxide SCL detection method with a linear range of 0.5-50 µM and a detection limit of 0.32 µM is established. Moreover, the device can achieve the detection of glucose oxidase (GOD) activity and glucose by enzymatic conversion of glucose to hydrogen peroxide. The linear range of GOD detection is 1-200U/L with a detection limit of 0.86 U/L. The linear range of glucose detection is 0.5-70 µM with a detection limit of 0.43 µM. The cheap (a few dollars) and user-friendly apertureless USB-PUT is promising for sonochemistry applications and chemical education.

Silicotungstic acid as a highly efficient coreactant for luminol chemiluminescence for sensitive detection of uric acid.

Herein, we report luminol-silicotungstic acid (STA) chemiluminescence (CL) for the first time. The luminol-STA system resulted in remarkable CL enhancement (65 times) compared with the known classical luminol-H2O2 system because of the generation of the strong oxidizing agent tungsten trioxide from STA. Based on the quenching effect of uric acid, the new CL system is applied for the sensitive and selective assay of uric acid in its pure state (LOD 0.75 nM) and in real human urine with excellent recoveries in the range of 99.6-102.3%. Furthermore, this system permits the efficient detection of STA (LOD, 0.24 µM).

Turn-on fluorescent glutathione detection based on lucigenin and MnO2 nanosheets.

In this work, a glutathione (GSH) sensing nano-platform using lucigenin as a fluorescent probe in the presence of MnO2 nanosheets was reported for the first time. Unlike the earlier fluorescent detection systems based on MnO2 nanosheets, which depend on Förster resonance energy transfer (FRET) or the dynamic quenching effect (DQE), the mechanism of the quenching process of MnO2 nanosheets on lucigenin fluorescence was attributed mainly to a static quenching effect (SQE) with a minor contribution of the inner filter effect (IFE). A double exponential fluorescence decay of lucigenin was obtained in various MnO2 nanosheet concentrations as a result of their SQE and IFE. Based on this phenomenon and taking advantage of the redox reaction between GSH and MnO2 nanosheets, we have developed a switch-on sensitive fluorescent method for GSH via the recovery of the MnO2 nanosheet-quenched fluorescence of lucigenin. A good linearity range of 1.0-150.0 µM with a low limit of detection (S/N = 3) of 180.0 nM was achieved, revealing the higher sensitivity for GSH determination in comparison with the previously reported MnO2 nanosheet-based turn-on fluorescent methods. The developed fluorescent nano-platform exhibits excellent selectivity with successful application for GSH detection in human serum plasma, indicating its good practicability for GSH sensing in biological and clinical applications.