Graphene Quantum Dots‐based Electrochemical Biosensor for Catecholamine Neurotransmitters Detection

An useful electrochemical sensing approach was developed for epinephrine (EP) detection based on graphene quantum dots (GQDs) and laccase modified glassy carbon electrodes (GC). The miniature GC biosensor was designed and constructed via the immobilization of laccase in an electroactive layer of the electrode coated with carbon nanoparticles. This sensing arrangement utilized the catalytic oxidation of EP to epinephrine quinone. The detection process was based on the oxidation of catecholamine in the presence of the enzyme – laccase. With the optimized conditions, the analytical performance demonstrated a high degree of sensitivity −2.9 μA mM⁻¹ cm⁻², selectivity in a broad linear range (1–120×10⁻⁶ M) with detection limit of 83 nM. Moreover, the method was successfully applied for EP determination in labeled pharmacological samples.     

Development of an Electrochemical Biosensor for the Rapid Detection of Saxitoxin Based on Air Stable Lipid Films with Incorporated Anti‐STX Using Graphene Electrodes

A miniaturized potentiometric saxitoxin sensor on graphene nanosheets with incorporated lipid films and Anti‐STX, the natural saxitoxin receptor, immobilized on the stabilized lipid films is described in the present paper. An adequate selectivity for detection over a wide range of toxin concentrations, fast response time of ca. 5–20 min, and detection limit of 1 nM have been achieved. The proposed sensor is easy to construct and exhibits good reproducibility, reusability, selectivity, long shelf life and high sensitivity of ca. 60 mV/decade of toxin concentration. The method was implemented and evaluated in lake water and shellfish samples. This novel ultrathin film technology is currently adapted to the rapid detection of other toxins that could be used in bioterrorism.     

Electrochemical Sensor for Ultrasensitive Determination of Doxorubicin and Methotrexate Based on Cyclodextrin‐Graphene Hybrid Nanosheets

In this work, an electrochemical sensor based on a cyclodextrin‐graphene hybrid nanosheets modified glassy carbon electrode (CD‐GNs/GCE) was proposed for the ultrasensitive determination of doxorubicin and methotrexate. The peak currents of doxorubicin and methotrexate on the CD‐GNs/GCE increased 26.5 and 23.7 fold, respectively, compared to the results obtained on the bare GCE. Under optimized conditions, the linear response ranges for doxorubicin and methotrexate are 10 nM–0.2 µM and 0.1 µM–1.0 µM, with detection limits of 0.1 nM and 20 nM, respectively. The sensor showed the advantages of simple preparation, low cost, high sensitivity, good stability and reproducibility. These properties make the prepared sensor a promising tool for the determination of trace amounts of doxorubicin and methotrexate in biological, clinical and pharmaceutical fields.     

Electrochemical Biosensor for Naphthalene Acetic Acid in Fruits and Vegetables Based on Lipid Films with Incorporated Auxin‐binding Protein Receptor Using Graphene Electrodes

The present work describes a miniaturized potentiometric naphthalene acetic acid (NAA) sensor on graphene nanosheets with incorporated lipid films. Auxin‐binding protein 1 receptor immobilized on the stabilized lipid films provided adequate selectivity for detection over a wide range of hormone concentrations, fast response time of ca. 5 min, and detection limit of 10 nM. The proposed sensor is easy to construct and exhibits good reproducibility, reusability, selectivity, long shelf life and high sensitivity of ca. 56 mV/decade of hormone concentration. The reliability of the biosensor was successfully evaluated using a wide range of NAA‐spiked fruits and vegetables.     

Separation/Concentration‐signal‐amplification in‐One Method Based on Electrochemical Conversion of Magnetic Nanoparticles for Electrochemical Biosensing

We propose a separation/concentration‐signal‐amplification in‐one method based on electrochemical conversion (ECC) of magnetic nanoparticles (MNPs) to develop a facile and sensitive electrochemical biosensor for chloramphenicol (CAP) detection. Briefly, aptamer‐modified magnetic nanoparticles (MNPs‐Apt) was designed to capture CAP in sample, then the MNPs‐Apt composite was conjugated to Au electrode through the DNA hybridization between the unoccupied aptamer and a strand of complementary DNA. The ECC method was applied to transfer MNPs labels to electrochemically active Prussian blue (PB). The anodic and cathodic currents of PB were taken for signal readout. Comparing with conventional methods that require electrochemically active labels and related sophisticated labelling procedures, this method explored and integrated the magnetic and electrochemical properties of MNPs into one system, in turn realized magnetic capturing of CAP and signal generation without any additional conventional labels. Taking advantages of the high abundance of iron content in MNPs and the refreshing effect deriving from ECC process, the method significantly promoted the signal amplification. Therefore, the proposed biosensors exhibited linear detection range from 1 to 1000 ng mL⁻¹ and a limit of detection down to 1 ng mL⁻¹, which was better than or comparable with those of most analogues, as well as satisfactory specificity, storage stability and feasibility for real samples. The developed method may lead to new concept for rapid and facile biosensing in food safety, clinic diagnose/therapy and environmental monitoring fields.     

Development of an Electrochemical Biosensor for the Rapid Detection of Cholera Toxin Based on Air Stable Lipid Films with Incorporated Ganglioside GM1 Using Graphene Electrodes

The present work describes a miniaturized potentiometric cholera toxin sensor on graphene nanosheets with incorporated lipid films. Ganglioside GM1, the natural cholera toxin receptor, immobilized on the stabilized lipid films, provided adequate selectivity for detection over a wide range of toxin concentrations, fast response time of ca. 5 min, and detection limit of 1 nM. The proposed sensor is easy to construct and exhibits good reproducibility, reusability, selectivity, long shelf life and high sensitivity of ca. 60 mV/decade of toxin concentration. The method was implemented and validated in lake water samples. This novel ultrathin film technology is currently adapted to the rapid detection of other toxins that could be used in bioterrorism.     

纳米材料在电化学生物传感器及生物电分析领域中的应用

纳米尺度上的生物分析化学是当今国际生物分析领域研究的前沿和热点.该文阐述了纳米粒子在电化学免疫传感器及电化学DNA传感器领域的应用,着重介绍了以纳米材料为载体设计新型的具有生物分子识别和电信号增强作用的纳米标记粒子在构建高灵敏电化学生物传感器以及多组分同时检测中的应用.     

A New Electrochemical Biosensor for Determination of Hydrogen Peroxide in Food Based on Well‐Dispersive Gold Nanoparticles on Graphene Oxide

Herein, we describe a new method for the detection of hydrogen peroxide (H₂O₂) in food by using an electrochemical biosensor. Initially, ultrafine gold nanoparticles dispersed on graphene oxide (AuNP‐GO) were synthesized by the redox reaction between AuCl₄^? and GO, and thionine‐catalase conjugates were then assembled onto the AuNP‐GO surface on a glassy carbon electrode. With the aid of the AuNP‐GO, the as‐prepared biosensor exhibited good electrocatalytic efficiency toward the reduction of H₂O₂ in pH 5.8 acetic acid buffer. Under optimal conditions, the dynamic responses of the biosensor toward H₂O₂ were achieved in the range from 0.1 µM to 2.3 mM, and the detection limit (LOD) was 0.01 µM at 3s_B. The Michaelis–Menten constant was measured to be 0.98 mM. In addition, the repeatability, reproducibility, selectivity and stability of the biosensor were investigated and evaluated in detail. Finally, the method was applied for sensing H₂O₂ in spiked or naturally contaminated samples including sterilized milk, apple juices, watermelon juice, coconut milk, and mango juice, receiving good correspondence with the results from the permanganate titration method. The disposable biosensor could offer a great potential for rapid, cost‐effective and on‐field analysis of H₂O₂ in foodstuff.     

Synthesis of Silver Nanoparticle‐Graphene Composites for Electroanalysis Applications using Chemical and Electrochemical Methods

An electrochemical device was developed for the simultaneous determination of sulfamethoxazole (SMX) and trimethoprim (TMP) using differential pulse voltammetry and glassy carbon (GC) electrodes modified with reduced graphene oxide (rGO) and silver nanoparticle (AgNP) composites, synthesised using both chemical and electrochemical methods. The morphology and electrochemical behaviour of the GC electrodes modified with the rGO/AgNP (chemical method) and rGO‐AgNP (electrochemical method) composites were characterised by scanning electron microscopy and cyclic voltammetry. These techniques demonstrated that, in both methods, the graphene oxide was modified by the AgNPs, and the composite synthesised by the electrochemical method showed a better dispersion of the nanoparticles, resulting in an increase in the surface area compared to the rGO/AgNP composite. The GC/rGO‐AgNP electrode was evaluated and optimised for the simultaneous determination of SMX and TMP, achieving detection limits of 0.6 μmol L⁻¹ for the SMX and 0.4 μmol L⁻¹ for the TMP. The proposed GC/rGO‐AgNP electrochemical device was successfully applied to the simultaneous determination of SMX and TMP in wastewaters samples.     

A Facile Graphene Nanosheets‐based Electrochemical Sensor for Sensitive Detection of Honokiol in Traditional Chinese Medicine

The sensitive detection of honokiol was performed using a graphene nanosheets‐based electrochemical sensor by cyclic voltammogram and a differential pulse anodic stripping voltammogram. Several important parameters such as deposition cycle of reduced graphene oxide, the acidity of the running buffer, accumulation potential and accumulation time were investigated to acquire the optimum conditions. The sensor was further applied to quantification of honokiol in the concentration range from 0.005 to 10 µM with a low detection limit of 1.7 nM. Finally, the sensor successfully determined the content of honokiol in Ageratum Liquid with a satisfied recovery of 98.2 %～99.1 %.     

青霉素酶-氧化苏木精修饰Au/ZnO/石墨烯基青霉素电化学传感器的研制

采用均匀沉淀法合成ZnO纳米颗粒( ZnO NPs),以ZnO NPs为种子,制备水溶性Au/ZnO异质结构。将Au/ZnO异质结构附着于离子液体功能化石墨烯( GN)复合膜上,形成一种新颖的负载型石墨烯复合材料(Au/ZnO/GN)。所构建的青霉素酶-氧化苏木精修饰Au/ZnO/GN(PH-AZG)传感器在PBS水溶液(pH=7.0)中对青霉素钠检测线性范围为2.5×10-14~3.3×10-6 mol/L,检出限达到1.5×10-14 mol/L (S/N≥3)。在相同条件下制备5根PH-AZG电极,其响应电流的相对标准偏差(RSD)小于3.2%。同时,在实际牛奶制品中,本方法的检测线性范围为5×10-14~5×10-7 mol/L,加标回收率为99.7%~101.4%,RSD 为2.3%~3.5%(n=5)。结果表明,本方法对实际牛奶制品中低浓度青霉素钠的检测具有可行性。     

基于氧化石墨烯荧光适体传感器的胰岛素检测

采用荧光基团(FAM)标记的核酸适体作为识别元件,氧化石墨烯为淬灭剂,建立了一种高选择性、高灵敏度的核酸适体传感器.核酸适体与氧化石墨烯结合后,荧光淬灭,此时溶液无荧光;加入胰岛素后,溶液中荧光得到恢复.利用荧光分析法检测加入胰岛素前后,溶液中荧光强度的变化,获取了荧光适体传感器的线性度和灵敏度,实现对胰岛素浓度的测定.结果表明,在5×10-8 ～ 1×10-5 mol/L范围内,胰岛素的浓度与溶液中荧光强度有良好的线性关系,检出限为10 nmol/L.采用此方法检测胰岛素,操作简便,检测速度快,准确性高,选择性好,检出限低.     

Facile Fabrication of a Graphene‐based Electrochemical Biosensor for Glucose Detection

A simple and effective glucose biosensor based on immobilization of glucose oxidase (GOD) in graphene (GR)/Nafion film was constructed. The results indicated that the immobilized GOD can maintain its native structure and bioactivity, and the GR/Nafion film provides a favorable microenvironment for GOD immobilization and promotes the direct electron transfer between the electrode substrate and the redox center of GOD. The electrode reaction of the immobilized GOD shows a reversible and surface‐controlled process with the large electron transfer rate constant (k_s) of 3.42±0.08 s^?1. Based on the oxygen consumption during the oxidation process of glucose catalyzed by the immobilized GOD, the as‐prepared GOD/GR/Nafion/GCE electrode exhibits a linear range from 0.5 to 14 mmol·L^?1 with a detection limit of 0.03 mmol·L^?1. Moreover, it displays a good reproducibility and long‐term stability.     

Nanomaterials‐based Electrochemical Sensing of Cardiac Biomarkers for Acute Myocardial Infarction: Recent Progress

The development of the methods for early and accurate diagnosis of acute myocardial infarction are needed to facilitate immediate treatment of patients. One of the ways to achieve that is the detection of cardiac biomarkers for myocardial infarction, such as thrombin, cardiac troponins (I and T), myoglobin, etc. Nanotechnology has played an important role in the development of sensitive and efficient electrochemical sensors for cardiac biomarkers. In this review, we discuss recent progress on nanomaterial‐based electrochemical sensing of various cardiac biomarkers for acute myocardial infarction.     

A Review of Glucose Biosensors Based on Graphene/Metal Oxide Nanomaterials

In recent years, considerable attention has been paid to developing economical yet rapid glucose sensors using graphene and its composites. Recently, the excellent properties of graphene and metal oxide nanoparticles have been combined to provide a new approach for highly sensitive glucose sensors. This review focuses on the development of graphene functionalized with different nanostructured metal oxides (such as copper oxide, zinc oxide, nickel oxide, titanium dioxide, iron oxide, cobalt oxide, and manganese dioxide) for use as glucose biosensors. Additionally, a brief introduction of the electrochemical principles of glucose biosensors (including amperometric, potentiometric, and conductometric) is presented. Finally, the current status and future prospects are outlined for graphene/metal oxide nanomaterials in glucose sensing.     

DNA Electrochemical Aptasensor for Detecting Fumonisins B1 Based on Graphene and Thionine Nanocomposite

In this paper, a novel aptasensor was designed by with the dual amplification of Au nanoparticles (AuNPs) and graphene/thionine nanocomposites (GS‐TH) for sensitive determination of fumonisins B₁ (FB₁). AuNPs is modified at the electrode surface to increase the electrical conductivity and fabricate specific recognition interface for FB₁ through the hybridization of capture DNA and its aptamer. Large number of TH molecules were loaded at the surface of graphene sheet to served as electrochemical probe and increase its electrochemical signal due to the excellent conductivity and large surface area of graphene sheet. This type of nanocomposites is then assembled to the single strand section of FB₁ aptamer at electrode surface by π–π stacking interactions between them, leading to an enhanced electrochemical signal. After the specific combination between FB₁ aptamer and its target (FB₁) in solution, GS–TH was released from electrode surface, resulting in a decreased electrochemical signal. The result demonstrated that the decreased currents were proportional to the FB₁ concentration in the range of 1–10⁶ pg/mL with a detection limit of 1 pg/mL. Besides, the developed aptasensor was also applied successfully for the determination of FB₁ in feed samples. The result shows this aptasensor has a higher sensitivity and selectivity.     

An Electrochemical Sensing Platform Based on Graphene Oxide and Molecularly Imprinted Polymer Modified Electrode for Selective Detection of Amoxicillin

An electrochemical sensing platform based on composite material, consisting of molecularly imprinted polymer coated on graphene oxide (MIP-GO), was developed for selective and sensitive analysis of amoxicillin (AMOX). The MIP-GO composite, which was fabricated by sol-gel polymerization after removal of template molecule, was deposited as a thin film on glassy carbon electrode, and then was electrochemically characterized by cyclic voltammetry and differential pulse voltammetry. The linear response for the determination of AMOX was obtained in the concentration range from 5.0×10⁻¹⁰ to 9.1×10⁻⁷ M under the most proper conditions and the detection limit was found to be 2.94×10⁻¹⁰ M.     

Point‐of‐Care Smartphone‐based Electrochemical Biosensing

Point‐of‐care (PoC) biosensors offer promising solutions to today's adverse and costly healthcare issues by moving diagnostic tools closer to the patient. The ubiquity of smartphones has brought about an emergence of PoC devices, which leverage the smartphone's capabilities, enabling the creation of low‐cost and portable biosensors. Electrochemical biosensors are well suited for PoC testing since the transducers can be miniaturized and inexpensively fabricated. This review paper discusses recent developments in smartphone‐based electrochemical biosensors for PoC diagnostics. These peripherals utilize the various connectivity options (for example proprietary ports, audio headphone‐jack, or wireless radio) to offload functionality to the smartphone. The smartphone‐based implementations of various electrochemical techniques, such as amperometry, potentiometry, and impedance spectroscopy are explored. Major challenges include reducing power, area, and cost of measurement circuitry, while maintaining adequate performance for PoC diagnostic applications.     

Advantages of Carbon Nanomaterials in Electrochemical Aptasensors for Food Analysis

Electrochemical aptasensors appear as promising tools in food analysis, able to provide sensitive, fast and cost‐effective analysis, with the added advantage of portability. Carbon nanomaterials and in particular carbon nanotubes and graphene are among the nanomaterials most often used to build electrochemical aptasensors due to their good electrical conductivity, large surface area and multiple functionalisation possibilities. This review aims to give an overview of the types of carbon nanomaterials and their composites which have been used to enhance the performance of electrochemical aptasensors. Examples are detailed for the biosensors which were tested with real food samples. In these aptasensors, carbon nanomaterials have played different roles, from facilitating the immobilization of high amounts of aptamer and enhancing the electroactive area of the sensors to roles as nanocarrier for signaling probes in amplification schemes or even as electroactive probes generating the output signal. The survey of recent literature shows a positive evolution towards increased aptasensor testing with food samples. However, many challenges remain related to the better characterization of nanomaterials used, clarifying the roles of specific components in multi‐component nanocomposites and widening the types of food matrices and analytes tested with the aptasensors. Although we are still far from knowing when these novel tools will replace classic analytical methods in food analysis, carbon nanomaterials will certainly continue to play an important role in the design of future electrochemical aptasensors for food analysis.     

Graphene Based Electrochemical Sensors and Biosensors: A Review

Graphene, emerging as a true 2‐dimensional material, has received increasing attention due to its unique physicochemical properties (high surface area, excellent conductivity, high mechanical strength, and ease of functionalization and mass production). This article selectively reviews recent advances in graphene‐based electrochemical sensors and biosensors. In particular, graphene for direct electrochemistry of enzyme, its electrocatalytic activity toward small biomolecules (hydrogen peroxide, NADH, dopamine, etc.), and graphene‐based enzyme biosensors have been summarized in more detail; Graphene‐based DNA sensing and environmental analysis have been discussed. Future perspectives in this rapidly developing field are also discussed.