Research Surveys of Electrochemical Sensors for in-situ Determining Hydrogen in Steels

1. IntroductionThe source of hydrogen which causes failure in thepresence of stress can be a corrosive reaction, a hydrogen gas circumstance at elevated temperatures andhigh pressure or also a pretreatmellt process such aspickling, welding or a plating process j etc.Since the important role of hydrogen in the catastrophic failure of metal has been recognized, it is understandable that a great interest exists in developingmethods (preferably nondestructive) for determination of the hydrogen con…     

基于碳纳米材料的肾上腺素电化学传感器研究进展

肾上腺素(AD)作为一种神经递质在人体内扮演重要角色,其含量的高低直接影响人体身体健康,因此对AD进行快速检测具有重要的实际意义。其检测方法中电化学方法具有灵敏度高、检测速度快、操作简便的优点,因而构建性能优异的肾上腺素电化学传感器成为研究热点。为提高传感器的电化学性能,碳纳米材料被采纳作为修饰传感器的新型材料而广泛应用,取得了检测限低、灵敏度高并有希望应用于临床检测的巨大进步。本文从碳点、石墨烯、碳纳米颗粒等碳纳米材料出发,分析AD在电极表面的电氧化还原机制,对近年来基于碳纳米材料的肾上腺素电化学传感器制备方法及检测结果进行分类统计,并对今后的检测提出展望,以期获得更有效的肾上腺素电化学传感器。     

Influence of raw carbon nanotubes diameter for the optimization of the load composition ratio in epoxy amperometric composite sensors

In this work, it is reported the necessity to characterize the raw carbon materials before their application in composite electrodes based on multiwall carbon nanotubes (MWCNTs) dispersed in epoxy resin for the development of improved amperometric sensors. These sensors must contain an optimum MWCNT/epoxy ratio for their best electroanalytical response. The main drawback in MWCNTs composite materials resides in the lack of homogeneity of the different commercial nanotubes largely due to different impurities content, as well as dispersion in their diameter/length ratio and state of aggregation. The optimal composite electrode composition takes into account the high electrode sensitivity, low limit of detection, fast response, and electroanalytical reproducibility. These features depend on carbon nanotube physical properties as the diameter. Three different commercial carbon nanotubes with different diameters were characterized by transmission electron microscopy and the results were significantly different from the ones provided by the manufacturers. Then, the three MWCNTs were used for the MWCNT/epoxy sensors construction. After an accurate electrochemical characterization by cyclic voltammetry and electrochemical impedance spectroscopy, they were employed as working electrodes using ascorbic acid as a reference analyte. Percolation theory was applied in order to verify the electrochemical results. It is demonstrated that the optimum interval load of raw carbon material in the optimized-composite electrodes closely depends on the MWCNTs diameter, needing 5 % in carbon content for the narrowest MWCNTs containing composite electrodes versus 12 % for the widest MWCNTs.     

Progress of Solid Electrolytes and the Electrochemical Sensors

Four types of solid state electrochemical sensors and their general principles are introduced in the paper. The novel type-IV sensors developed in the last few years are emphasized to study hereafter. The ways to design new electrochemical sensors and the directions to develop new solid electrolytes for new electrochemical sensors are also discussed.     

Fabrication of cone-shaped boron doped diamond and gold nanoelectrodes for AFM-SECM

We demonstrate a reliable microfabrication process for a combined atomic force microscopy (AFM) and scanning electrochemical microscopy (SECM) measurement tool. Integrated cone-shaped sensors with boron doped diamond (BDD) or gold (Au) electrodes were fabricated from commercially available AFM probes. The sensor formation process is based on mature semiconductor processing techniques, including focused ion beam (FIB) machining, and highly selective reactive ion etching (RIE). The fabrication approach preserves the geometry of the original AFM tips resulting in well reproducible nanoscaled sensors. The feasibility and functionality of the fully featured tips are demonstrated by cyclic voltammetry, showing good agreement between the measured and calculated currents of the cone-shaped AFM-SECM electrodes.     

A potentiostat based on a voltage-controlled current source for usewith amperometric gas sensors

Amperometric gas-sensing devices develop a current that is proportional to the concentration of gas that is supplied to them. The circuit that maintains electrochemical stability in the sensor as well as buffering the current output is called a potentiostat. Some sensors used for gas sensing have very large electrode capacitances, which can result in instability with conventional potentiostat designs. The responses of two potentiostat designs to a gas were compared. One is based on conventional use of a current-to-voltage converter (CVC); the second is a new design which uses a voltage-controlled current source (VCCS). A frequency analysis of the VCCS potentiostat design is included     

Prediction for the separation efficiency of a pair of enantiomers during chiral high-performance liquid chromatography using a quartz crystal microbalance

A simple and rapid screening method of the chiral stationary phase during high-performance liquid chromatography (HPLC) utilizing a quartz crystal microbalance (QCM) has been developed for the chiral separation of a pair of enantiomers. The outline of the method is as follows: a self-assembled monolayer (SAM) is constructed on the gold electrodes of the QCM sensor chips by utilizing the interaction between thiols and gold. The chiral selectors used as chiral stationary phases in the HPLC are then immobilized, and a pseudostationary phase is constructed on the electrodes. Subsequently, the sensors are equilibrated in the solutions, the targeted chiral samples are injected, and the frequency changes are observed. Four kinds of chiral molecules and three kinds of chiral stationary phases were examined in this study. When chiral separation is possible using the chiral stationary phase immobilized on the sensors, significant differences in the frequency changes are observed because the intensities based on interactions differ among the isomers. The developed method can predict not only the possibility for chiral separation but also the elution order from the chiral stationary phase column. Furthermore, the degree of the mutual separation of a pair of enantiomers seems to be roughly predictable from the difference in the frequency change (DeltaF) and first-order association rate constant (k(obs)). The method does not require several different kinds of chiral columns that are more expensive than achiral ones such as the octadecylsilica (ODS) column. The required amounts of the chiral stationary phases are extremely small, and the sensors with immobilized chiral selectors are reusable. In addition, the method requires only a few minutes to complete the analysis. Thus, considerable reductions in both cost and time are realized. By applying the developed method to many chiral molecules and chiral stationary phases, its superiority may be corroborated; thus, it is expected that the method can be effectively used for the selection of chiral stationary phases.     

Emerging biomedical sensing technologies and their applications

Recent progress in biomedical sensing technologies has resulted in the development of several novel sensor products and new applications. Modern biomedical sensors developed with advanced microfabrication and signal processing techniques are becoming inexpensive, accurate, and reliable. A broad range of sensing mechanisms has significantly increased the number of possible target measurands that can be detected. The miniaturization of classical "bulky" measurement techniques has led to the realization of complex analytical systems, including such sensors as the BioChemLab-on-a-Chip. This rapid progress in miniature devices and instrumentation development will significantly impact the practice of medical care as well as future advances in the biomedical industry. Currently, electrochemical, optical, and acoustic wave sensing technologies have emerged as some of the most promising biomedical sensor technologies. In this paper, important features of these technologies, along with new developments and some of the applications, are presented.     

Chiral Responsive Liquid Quantum Dots

How to convert the weak chiral‐interaction into the macroscopic properties of materials remains a huge challenge. Here, this study develops highly fluorescent, selectively chiral‐responsive liquid quantum dots (liquid QDs) based on the hydrophobic interaction between the chiral chains and the oleic acid‐stabilized QDs, which have been designated as (S)‐1810‐QDs. The fluorescence spectrum and liquidity of thermal control demonstrate the fluorescence properties and the fluidic behavior of (S)‐1810‐QDs in the solvent‐free state. Especially, (S)‐1810‐QDs exhibit a highly chiral‐selective response toward (1R, 2S)‐2‐amino‐1,2‐diphenyl ethanol. It is anticipated that this study will facilitate the construction of smart chiral fluidic sensors. More importantly, (S)‐1810‐QDs can become an attractive material for chiral separation.     

Toward Smart Sensing by MXene (Small 14/2023)

The Internet of Things era has promoted enormous research on sensors, communications, data fusion, and actuators. Among them, sensors are a prerequisite for acquiring the environmental information for delivering to an artificial data center to make decisions. The MXene-based sensors have aroused tremendous interest because of their extraordinary performances. In this review, the electrical, electronic, and optical properties of MXenes are first introduced. Next, the MXene-based sensors are discussed according to the sensing mechanisms such as electronic, electrochemical, and optical methods. Initially, biosensors are introduced based on chemiresistors and field-effect transistors. Besides, the wearable pressure sensor is demonstrated with piezoresistive devices. Third, the electrochemical methods include amperometry and electrochemiluminescence as examples. In addition, the optical approaches refer to surface plasmonic resonance and fluorescence resonance energy transfer. Moreover, the prospects are delivered of multimodal data fusion toward complicated human-like senses. Eventually, future opportunities for MXene research are conveyed in the new material discovery, structure design, and proof-of-concept devices.     

Electrochemical and optical sugar sensors based on phenylboronic acid and its derivatives

Recent progress in electrochemical and optical sugar sensors based on phenylboronic acid (PBA) and its derivatives as recognition components is reviewed. PBAs are known to bind diol compounds including sugars to form cyclic boronate esters that are negatively charged as a result of the addition of OH^? ions from solution. Based on the formation of PBA charged species, sugars and their derivatives can be detected by means of electrochemical and optical techniques. For the development of PBA-based electrochemical sensing systems or sensors, PBA is modified with a redox-active marker, because PBA itself is electrochemically inactive, and ferrocene derivatives are often employed for this purpose. Ferrocene-modified PBAs have been used as redox-active additives in solution for the electrochemical detection of sugars and derivatives. PBA-modified electrodes have also been constructed as reagentless electrochemical sensors, where PBAs are immobilized on the surface of metal and carbon electrodes through mainly two routes: as a self-assembled monolayer film and as a polymer thin film. PBA-modified electrodes can be successfully used to detect sugars and derivatives through potentiometric and voltammetric responses. In addition, PBA-modified electrodes can be used for the immobilization of glycoenzymes on an electrode surface by the formation of boronate esters with carbohydrate chains in the glycoenzymes, thus resulting in enzyme biosensors. For the development of PBA-based optical sensors, a variety of chromophores and fluorophores have been coupled with PBA. Azobenzene dyes have been most frequently used for the preparation of colorimetric sugar sensors, in which the absorption wavelength and intensity of the dye are dependent on the type and concentration of added sugars. The sensitivity of the sensors is significantly improved based on multi-component systems in which alizalin red S, pyrocatechol violet, starch–iodine complex, and cyclodextrin are employed as indicators. Anthracene, pyranine, fluorescein, and rhodamine dyes have been used as fluorophores for fluorescence sensors. These dyes have been used in solution or immobilized in films, hydrogels, nanospheres, and quantum dots (QDs) to enhance the sensitivity. QDs-based sensors have been successfully applied for continuous monitoring of glucose in cells. Holographic glucose sensors have also been developed by combining PBA-immobilized hydrogels and photonic crystal colloidal arrays.     

纳米材料在电化学传感器检测抗生素中的应用进展

抗生素自发现至今,由于其可以阻碍细菌的生长,被广泛应用于预防和治疗细菌的感染疾病上。但是抗生素在畜牧业、农业等方面的滥用滥排导致抗生素污染,极大地威胁水源地的安全,导致细菌耐药性增强、给环境及人类健康带来重大的危害。因此,抗生素的检测近年来得到了广泛的关注,而大多抗生素都具有电化学活性。基于此,纳米修饰电极可以使抗生素在电解质中的电化学氧化或还原反应增强,从而促进其灵敏度的提高,使电化学传感器可以检测到各类抗生素。本文详细介绍了用于检测抗生素的各种纳米材料修饰电极的电化学传感器及其性能。最后,讨论了纳米材料电化学传感器在抗生素检测中面临的挑战和发展前景。     

Response characteristics of a reversible electrochemical sensor for the polyion protamine

We describe here in detail the first reversible electrochemical sensors for the polyion protamine. Potentiometric sensors were proposed in recent years, mainly for the determination of the polyions heparin and protamine. Such potentiometric polyion sensors functioned on the nonequilibrium extraction of polyions into a hydrophobic membrane phase via ion pairing with lipophilic ion exchangers. This made it difficult to design sensors that operate in a truly reversible fashion. The reversible sensors described here utilize the same basic response mechanism as their potentiometric counterparts, but the processes of extraction and ion stripping are now fully controlled electrochemically. Spontaneous polyion extraction is avoided by using membranes containing highly lipophilic electrolytes that possess no ion-exchange properties. Reversible extraction of polyions is induced if a constant current pulse of fixed duration is applied across the membrane, followed by a baseline potential pulse. The key theoretical response principles of this new class of polyion sensors are discussed here and compared to those of its classical potentiometric counterpart. The electrochemical sensing system is characterized in terms of optimal working conditions, membrane composition, selectivity, and influence of sample stirring and organic-phase diffusion coefficient on the response characteristics. Excellent potential stability and reversibility of the sensors are observed, and measurements of heparin concentration in whole blood samples via protamine titration are demonstrated.     

Chiral Materials: Progress,Applications, and Prospects

Chirality is a universal phenomenon in molecular and biological systems, denoting an asymmetric configurational property where an object cannot be superimposed onto its mirror image by any kind of translation or rotation, which is ubiquitous on the scale from neutrinos to spiral galaxies. Chirality plays a very important role in the life system. Many biological molecules in the life body show chirality, such as the “codebook” of the earth's biological diversity-DNA, nucleic acid, etc. Intriguingly, living organisms hierarchically consist of homochiral building blocks, for example, l -amino acids and d -sugars with unknown reason. When molecules with chirality interact with these chiral factors, only one conformation favors the positive development of life, that is, the chiral host environment can only selectively interact with chiral molecules of one of the conformations. The differences in chiral interactions are often manifested by chiral recognition, mutual matching, and interactions with chiral molecules, which means that the stereoselectivity of chiral molecules can produce changes in pharmacodynamics and pathology. Here, the latest investigations are summarized including the construction and applications of chiral materials based on natural small molecules as chiral source, natural biomacromolecules as chiral sources, and the material synthesized by design as a chiral source.     

Ionic‐Liquid‐Assisted Sonochemical Synthesis of Carbon‐Nanotube‐Based Nanohybrids: Control in the Structures and Interfacial Characteristics

A versatile, facile, and rapid synthetic method of advanced carbon nanotube (CNT)‐based nanohybrid fabrication, or the so‐called ionic‐liquid‐assisted sonochemical method (ILASM), which combines the supramolecular chemistry between ionic liquids (ILs) and CNTs with sonochemistry for the control in the size and amount of uniformly decorated nanoparticles (NPs) and interfacial engineering, is reported. The excellence in electrocatalysis of hybrid materials with well‐designed nanostructures and favorable interfaces is demonstrated by applying them to electrochemical catalysis. The synthetic method discussed in this report has an important and immediate impact not only on the design and synthesis of functional hybrid nanomaterials by supramolecular chemistry and sonochemistry but also on applications of the same into electrochemical devices such as sensors, fuel cells, solar cells, actuators, batteries, and capacitors.     

Ceramics for chemical sensing

Many types of sensors have been developed to detect chemical species in the gas phase. These include optical based on color change or fluoresence, surface acoustic wave (SAW) devices, electrochemical, chemoresistive/semiconductive, field effect transistors (FET), metal-insulator-semiconductor (MIS) diode devices, and many other. Among these, resistive type sensors based on ceramic oxides are particularly attractive because of their low cost, wide range of applications and potential for use in electronic nose. This article focuses mainly on the resistive/semiconductive, especially the surface conductive ceramic oxide type gas sensors. The main emphasis is on the basic principles involving gas-solid reactions. Also discussed are selected applications with an emphasis on sensor design issues. Since SnO₂ can be used as a model system for oxide-based sensors, most of the discussions focuses on this system, though other systems are occasionally highlighted illustrating recent developments.     

Single-Site Sn?O?Cu Pairs with Interfacial Electron Transfer Effect for Enhanced Electrochemical Catalysis and Sensing

As advanced electrochemical catalysts, single-atom catalysts have made great progress in the field of catalysis and sensing due to their high atomic utilization efficiency and excellent catalytic performance. Herein, stannum-doped copper oxide (CuO Sn₁) nanosheets with single-site Sn O Cu pairs as active sites are synthesized as electrocatalysts for biological molecule detection. Compared with CuO-based electrochemical sensors, the CuO Sn₁-based electrochemical sensors have improved detection sensitivity with a rapid electrochemical response. Theoretical calculation reveals that the single-site Sn O Cu pairs induced interfacial electronic transfer effect can strengthen hydroxy adsorption and thus reduce the energy barrier of the biological molecule oxidation process. As a concept application, electrochemical detection of dopamine and uric acid molecules is achieved, exhibiting satisfactory sensitivity and selectivity. This work demonstrates the advantages of single-site Sn O Cu pairs in electrochemical catalysis and sensing, which provides theoretical guidance for understanding the structure-activity relationship for sensitive electrochemical sensing.     

Sensitive determination of uric acid by using graphene quantum dots as a new substrate for immobilisation of uric oxidase

A novel strategy for highly sensitive electrochemical detection of uric acid (UA) was proposed based on graphene quantum dots (GQDs), GQDs were introduced as a suitable substrate for enzyme immobilisation. Uric oxidase (UOx) was immobilised on GQDs modified glassy carbon electrode (GCE). Transmission electron microscope, scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy techniques were used for characterising the electrochemical biosensor. The developed biosensor responds efficiently to UA presence over the concentration linear range 1–800 μM with the detection limit 0.3 μM. This novel biosensing platform based on UOx/GQDs electrode responded even more sensitively than that based on GCE modified by UOx alone. The inexpensive, reliable and sensitive sensing platform based on UOx/GQDs electrode provides wide potential applications in clinical.Inspec keywords: organic compounds, graphene devices, quantum dots, enzymes, biosensors, biochemistry, electrochemical electrodes, electrochemical sensors, transmission electron microscopy, scanning electron microscopy, voltammetry (chemical analysis), electrochemical impedance spectroscopy, nanomedicine, molecular biophysicsOther keywords: sensitive uric acid determination, graphene quantum dots, uric oxidase immobilisation, electrochemical detection, GQD, enzyme immobilisation, glassy carbon electrode, GCE, transmission electron microscope, scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectroscopy, electrochemical biosensor, C     

Response of electrochemical oxygen sensors to inert gas-air and carbon dioxide-air mixtures: measurements and mathematical modelling

Electrochemical oxygen gas sensors are widely used for monitoring the state of inertisation of flammable atmospheres and to warn of asphyxiation risks. It is well established but not widely known by users of such oxygen sensors that the response of the sensor is affected by the nature of the diluent gas responsible for the decrease in ambient oxygen concentration. The present work investigates the response of electrochemical sensors, with either acid or alkaline electrolytes, to gas mixtures comprising air with enhanced levels of nitrogen, carbon dioxide, argon or helium. The measurements indicate that both types of sensors over-read the oxygen concentrations when atmospheres contain high levels of helium. Sensors with alkaline electrolytes are also shown to underestimate the severity of the hazard in atmospheres containing high levels of carbon dioxide. This deviation is greater for alkaline electrolyte sensors compared to acid electrolyte sensors. A Computational Fluid Dynamics (CFD) model is developed to predict the response of an alkaline electrolyte, electrochemical gas sensor. Differences between predicted and measured sensor responses are less than 10% in relative terms for nearly all of the gas mixtures tested, and in many cases less than 5%. Extending the model to simulate responses of sensors with acid electrolytes would be straightforward.     

Maltase Decorated by Chiral Carbon Dots with Inhibited Enzyme Activity for Glucose Level Control

Carbon dots (CDs) have attracted increasing attention in disease therapy owing to their low toxicity and good biocompatibility. Their therapeutic effect strongly depends on the CDs structure (e.g., size or functional groups). However, the impact of CDs chirality on maltase and blood glucose level has not yet been fully emphasized and studied. Moreover, in previous reports, chiral CDs with targeted optical activity have to be synthesized from precursors of corresponding optical rotation, severely limiting chiral CDs design. Here, chiral CDs with optical rotation opposite to that of the precursor are facilely prepared through electrochemical polymerization. Interestingly, their chirality can be regulated by simply adjusting reaction time. At last, the resultant (+)‐DCDs (700 µg mL^?1) are employed to modify maltase in an effort to regulate the hydrolytic rate of maltose, showing an excellent inhibition ratio to maltase of 54.7%, significantly higher than that of (?)‐LCDs (15.5%) in the same reaction conditions. The superior performance may be attributed to the preferable combination of DCDs with maltase. This study provides an electrochemical method to facilely regulate CDs chirality, and explore new applications of chiral CDs as antihyperglycemic therapy for controlling blood glucose levels.