Electrochemical Determination of Hydrogen Peroxide Using a Glassy Carbon Electrode Modified with Three-Dimensional Copper Hydroxide Nanosupercages and Electrochemically Reduced Graphene Oxide

Three-dimensional copper hydroxide nanosupercages and electrochemically reduced graphene oxide were used to modify the glassy carbon electrode for the selective determination of hydrogen peroxide. The morphology and electrochemistry properties of copper hydroxide nanosupercage/electrochemically reduced graphene oxide/glassy carbon electrode were characterized using transmission electron microscopy, scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectra, Raman spectra, cyclic voltammetry, and electrochemical impedance spectroscopy. The resulting copper hydroxide nanosupercage/electrochemically reduced graphene oxide/glassy carbon electrode showed favorable performance for the electrocatalytic reduction of hydrogen peroxide. The amperometric current–time curve of the electrochemical sensor exhibited a wide linear range from 0.5 to 1030?µM with a limit of detection of 0.23?µM at a signal-to-noise ratio of three. Moreover, the sensor provided favorable selectivity, reproducibility, and stability and was used for the determination of H₂O₂ in tap water.     

Multifunctionality of Reduced Graphene Oxide in Bioderived Polylactide/Poly(Dodecylene Furanoate) Nanocomposite Films

This work reports on the first attempt to prepare bioderived polymer films by blending polylactic acid (PLA) and poly(dodecylene furanoate) (PDoF). This blend, containing 10 wt% PDoF, was filled with reduced graphene oxide (rGO) in variable weight fractions (from 0.25 to 2 phr), and the resulting nanocomposites were characterized to assess their microstructural, thermal, mechanical, optical, electrical, and gas barrier properties. The PLA/PDoF blend resulted as immiscible, and the addition of rGO, which preferentially segregated in the PDoF phase, resulted in smaller (from 2.6 to 1.6 µm) and more irregularly shaped PDoF domains and in a higher PLA/PDoF interfacial interaction, which suggests the role of rGO as a blend compatibilizer. rGO also increased PLA crystallinity, and this phenomenon was more pronounced when PDoF was also present, thus evidencing a synergism between PDoF and rGO in accelerating the crystallization kinetics of PLA. Dynamic mechanical thermal analysis (DMTA) showed that the glass transition of PDoF, observed at approx. 5 °C, shifted to a higher temperature upon rGO addition. The addition of 10 wt% PDoF in PLA increased the strain at break from 5.3% to 13.0% (+145%), and the addition of 0.25 phr of rGO increased the tensile strength from 35.6 MPa to 40.2 MPa (+13%), without significantly modifying the strain at break. Moreover, rGO decreased the electrical resistivity of the films, and the relatively high percolation threshold (between 1 and 2 phr) was probably linked to the low aspect ratio of rGO nanosheets and their preferential distribution inside PDoF domains. PDoF and rGO also modified the optical transparency of PLA, resulting in a continuous decrease in transmittance in the visible/NIR range. Finally, rGO strongly modified the gas barrier properties, with a remarkable decrease in diffusivity and permeability to gases such as O₂, N_2, and CO₂. Overall, the presented results highlighted the positive and sometimes synergistic role of PDoF and rGO in tuning the thermomechanical and functional properties of PLA, with simultaneous enhancement of ductility, crystallization kinetics, and gas barrier performance, and these novel polymer nanocomposites could thus be promising for packaging applications.     

基于中空多孔金纳米/石墨烯复合纳米材料的葡萄糖氧化酶直接电化学及其生物传感研究

采用溶液相牺牲模板法制备中空多孔金纳米粒子（HPAuNPs）,并将该材料与还原氧化石墨烯（rGO）复合,用于葡萄糖氧化酶（GOx）在玻碳电极（GCE）表面的有效固定,构建GOx/HPAuNPs/rGO/GCE传感界面。利用扫描和透射电镜、X射线光电子能谱、X射线衍射谱、红外光谱及电化学等方法对材料的形貌与结构,GOx的固定化过程,以及传感器的直接电化学和电催化性能进行表征。结果表明,HPAuNPs和rGO的协同作用能有效促进GOx与电极之间的直接电子转移（DET）。基于GOx/HPAuNPs/rGO/GCE对葡萄糖的良好电催化性能,该方法有效实现了对葡萄糖的高灵敏度检测,其电流响应的线性范围为0.05～7.0 mmol/L,检出限（S/N=3）为16μmol/L。该传感器具有良好的选择性、重现性及稳定性,对实际样品血清中血糖的测定结果令人满意,回收率为98.0%～103%,相对标准偏差不大于5.0%。     

Reduced Graphene Oxide/Poly(3‐hexylthiophene) Supramolecular Composites

Poly(3‐hexylthiophene) (P3HT) supramolecular structures are fabricated on P3HT‐dispersed reduced graphene oxide (RGO) monolayers and surfactant‐free RGO monolayers. P3HT is able to disperse RGO in hot anisole/N,N‐dimethylformamide solvents, and forms nanowires on RGO surfaces through a RGO induced crystallization process. The TEM and AFM investigation of the resultant P3HT/RGO composites shows that P3HT nanowires grow from RGO, and connect individual RGO monolayers. Raman spectroscopy confirms the interaction between P3HT and RGO, which allows the manipulation of the RGO electrical properties. Such a bottom‐up approach provides interesting graphene‐based composites for nanometer‐scale electronics.

     

Preparation and Its Application of Novel Graphene/Gold/Functional Conducting Polymer/Hydrogen Peroxide Biosensor

石墨烯材料和酶的固定对石墨烯基生物传感器性能及应用至关重要.金电极依次放入氧化石墨（0.05 mg/mL）和氯金酸（0.05 mmol/L）溶液中进行控制电位电解,循环以上操作20次后,转移至2,5-二（2-噻吩）-1-对苯甲酸吡咯单体溶液采用循环伏安法进行电聚合形成含有羧基的导电高分子膜,然后以1-（3-二甲氨基丙基）-3-乙基碳二亚胺盐酸盐（EDC）/N-羟基琥珀酰亚胺（NHS）为活化剂将辣根过氧化物酶共价键合在修饰电极表面制备过氧化氢生物传感器.研究表明,交替电沉积得到的石墨烯/金纳米复合材料分散性好,所制备的生物传感器对过氧化氢的氧化还原过程有显著的催化作用.过氧化氢浓度在2～200 nmol/L之间传感器的电流响应与浓度呈线性关系,相关系数（R2）为0.9996,方法的检测限是0.67 nmol/L（S/N=3）,灵敏度明显优于现有文献报道.此外,共价键合方式固定酶使传感器的稳定性和方法的重现性大大提高.5 nmol/L的过氧化氢溶液测定20次,相对标准偏差为1.2%.在4℃下储藏3个月传感器电化学响应变化值少于3%.该方法已成功应用于牛奶样品中痕量过氧化氢的测定.     

还原氧化石墨烯/金纳米修饰电极在新冠病毒检测中的应用

研究使用电化学沉积法在丝网印刷碳电极表面制备了还原氧化石墨烯和金纳米颗粒,构建了一种用于新冠病毒检测的石墨烯电化学传感器。通过扫描电子显微镜(SEM)和相应的电化学方法对纳米复合材料在电极表面的成功修饰进行了表征分析。并采用差分脉冲伏安法对传感器的性能进行检测,实验构建的电化学传感器具有良好的灵敏度,该传感器检线性范围为10_-10^-10_-6^mol/L,具有良好的重复性和特异性。     

Electrochemical Detection of Artemisinin Using Cobalt Sulphide/Reduced Graphene Oxide Nanocomposite

Solvothermally synthesized cobalt sulphide/reduced graphene oxide (CoS/rGO) was used to fabricate an electrochemical sensor for detection of artemisinin. Microscopic techniques were used to characterize CoS/rGO nanocomposite. The electrochemical sensor was fabricated by modifying the surface of glassy carbon electrode with CoS/rGO nanocomposite. [Fe(CN)6]^3−/4− was used as a mediator to aid oxidation of artemisinin. Differential pulse voltammetric technique was used for the detection of artemisinin. A linear range of 30–100 μM was used. Experimentally, a detection limit of 0.5 μM was obtained. Therefore, the developed sensor can be used for quality control of artemisinin.     

Reduced Graphene Oxide Nanocomposite Modified Electrodes for Sensitive Detection of Ciprofloxacin

The synthesis of novel nanocomposites with great sensing enhancement has played an important role in analytical chemistry, especially in the electrochemical detection of drug molecules. In this work, we report a wet chemical method for the preparation of a gold nanoparticle coated β‐cyclodextrin functionalized reduced graphene oxide nanocomposite. A number of different analytical techniques including ultraviolet‐visible spectroscopy, fourier transform infrared spectroscopy, scanning electron microscope and energy dispersive X‐ray spectroscopy were employed to characterize the as‐synthesized nanocomposite. With excellent electrocatalytic properties and high supramolecular recognition ability, the as‐synthesized nanocomposite was used to modify a glassy carbon electrode surface for the sensitive determination of ciprofloxacin using voltammetric technique. The current response of ciprofloxacin on the nanocomposite modified electrode was greatly enhanced compared to that on the bare and other modified electrodes. Using differential pulse voltammetry, the oxidation peak currents increased linearly with the ciprofloxacin concentrations in the range between 0.01 to 120 μM with a detection limit of 2.7 nM. The electrochemical testing results showed good stability and reproducibility. Therefore, the nanocomposite could be a potential candidate for the development of electrochemical sensors for sensitive and selective determination of ciprofloxacin or similar drugs in the future.     

In Situ Synthesis and Characterization of Poly(aryleneethynylene)‐Grafted Reduced Graphene Oxide

Using highly soluble bromo‐functionalized reduced graphene oxide (RGBr) as a key graphene template for surface‐directing Sonogashira–Hagihara polymerization, a novel soluble poly(arylene‐ethynylene)‐grafted reduced graphene oxide, hereafter abbreviated as PAE‐g‐RGO, was prepared in situ. The entirely different electron distribution of LUMO and HOMO of PAE‐g‐RGO suggested the existence of a charge‐transfer (CT) state (PAE^.?–RGO^.+). The negative ΔG_CS value (?2.57 eV) indicates that the occurrence of the charge separation via ¹RGO* in o‐DCB is exothermic and favorable. Upon irradiation with 365 nm light, the light‐induced electron paramagnetic resonance (LEPR) spectrum of PAE‐g‐RGO showed a decrease in the spin‐state density owing to photoinduced intramolecular electron transfer events in this system. A sandwich‐type Al/PAE‐g‐RGO/ITO device showed representative bistable electrical switching behavior. The nonvolatile memory performance was attributed to the CT‐induced conductance changes, which was supported by molecular computation results and conductive atomic force microscopy (C‐AFM) images.     

Preparation of Molecularly Imprinted Electrochemical Sensor for Detection of Vincristine Based on Reduced Graphene Oxide/Gold Nanoparticle Composite Film

An innovative molecularly imprinted electrochemical sensor was fabricated based on reduced graphene oxide (RGO) and gold nanocomposite (Au) for rapid detection of vincristine (VCR). The RGO‐Au composite membrane was obtained via direct one‐step electrodeposition technique of graphene oxide (GO) and chloroauric acid (HAuCl₄) on the surface of a glassy carbon electrode (GCE) by means of cyclic voltammetry (CV) in the potential range between ?1.5 and 0.6 V in phosphate buffer solution (PBS) of pH 9.18, which is capable of effectively utilizing its superior electrical conductivity, larger specific surface area due to its synergistic effect between RGO and Au. The molecularly imprinted polymers (MIPs) were synthesized on the RGO‐Au modified glassy carbon electrode surface with VCR as the template molecular, methyl acrylic acid (MAA) as the functional monomer, and ethylene glycol maleic rosinate acrylate (EGMRA) as a cross‐linker. The performance of the sensor was investigated by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) in detail. Under the optimum conditions, the fabricated sensor exhibited a linear relationship between oxidation peak current and VCR concentration over the range of 5.0×10^?8–5.0×10^?6 mol·L ^minus;1 with a correlation coefficient of 0.9952 and a detection limit (S/N=3) of 2.6×10^minus;8 mol·L^minus;1. The results indicated that the imprinted polymer films exhibited an excellent selectivity for VCR. The imprinted sensor was successfully used to determine VCR in real samples with recoveries of 90% –120% by using the standard addition method.     

Nickel oxide Nanoparticles/Carbon Nanotubes Nanocomposite for Non-enzymatic Determination of Hydrogen Peroxide

In this work, nickel oxide nanoparticles-modified multi-walled carbon nanotubes (CNTs) were prepared and used for H2O2 sensing application. Firstly, ex situ NiO nanoparticles (NPs) were prepared and further used to decorate polyethylenimine (PEI)-modified carboxylated CNTs. The obtained nanocomposite and its precursors were identified by using X-ray diffraction, thermal analysis, Raman spectroscopy and SEM and TEM images, N2 adsorption-desorption isotherms, and electrochemical techniques. The sensing properties of the NiO-modified nanocomposite toward H2O2 were studied by electrochemical techniques using glassy carbon electrodes (GCEs) as support material. After optimizing the sensor construction, the sensor sensitivity was about of 0.83±0.01 A M⁻¹ cm⁻² with a LOD of about 1.0 μM. In addition, it showed excellent anti-interference properties, reproducibility, and stability (over 4 months). Finally, such sensors were coupled to a flow injection device and the H2O2 concentration of some commercial antiseptic solutions were successfully obtained (with recovery ratios between 96.3–102.4 %).     

Prussian Blue/Reduced Graphene Oxide Composite for the Amperometric Determination of Dopamine and Hydrogen Peroxide

Prussian blue has significant application for the construction of electrochemical biosensors. In this work, Prussian blue-reduced graphene oxide modified glass carbon electrodes were successfully fabricated using electrochemical deposition. The high surface area of graphene oxide enhanced the deposition of Prussian blue and the resulting electrocatalytic activity. Infrared spectroscopy and scanning electron microscopy showed that the relatively porous Prussian blue was on the surface of reduced graphene oxide. Cyclic voltammetry showed that Prussian blue-coated reduced graphene oxide composite films improved electron transfer compared to Prussian blue films. The Prussian blue-reduced graphene oxide composite film provided higher response for the reduction of hydrogen peroxide and the oxidation of dopamine compared with the Prussian blue film due to synergistic effects between the reduced graphene oxide and Prussian blue particles. The sensitivity of the electrode was 0.1617 µA µM^?1 cm^?2. The linear dynamic range extended from 0.5 µM to 0.7 mM dopamine with a limit of detection equal to 125 nM. This work provided a versatile strategy for the design and construction of sensitive amperometric sensors with robust electrocatalytic behavior.     

具有高效电化学储能的中空网状笼还原氧化石墨烯

通过ZnO模板辅助电沉积法制备了中空网状笼还原氧化石墨烯,具有纳米管、多孔结构、网状结构和3D微米中空笼等多层次架构. 这样的结构能够同时促进电化学活性物种的传输,提高电极材料的利用率,以及提升超级电容器性能. 该类中空网状笼还原氧化石墨烯做超级充电器电极材料时表现出了优良的电化学性能,研究结果显示,在1.0 A•g^-1时比电容达到393 F•g^-1. 而且当电流密度从1.0 A•g^-1增加到20 A•g^-1,电容仅衰减了21.2%,10000周循环后比电容损失小于1%,表明具有优异的电容稳定性.     

Gold Nano Particle and Reduced Graphene Oxide Composite Modified Carbon Paste Electrode for the Ultra Trace Detection of Arsenic (III)

Gold nanoparticles (AuNPs) and reduced graphene oxide (RGO) composite modified carbon paste electrode (CPE) was prepared by electrodepositing AuNPs over the reduced graphene oxide (RGO) modified carbon paste electrode. The composite material was characterised using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) and atomic force microscopy (AFM) techniques. The nano composite modified electrode was applied for the determination of total As and for the inorganic speciation of As(III) and As(V) in environmental samples. The linear dynamic range was obtained for the determination of As(III) in the present method from 1μgL⁻¹ to 20 μgL⁻¹ and the limit of detection(LOD) in the standard solution was found to be 0.13 μgL⁻¹ for the 300 sec deposition time in 10 mL supporting electrolyte solution. This method was applied for the determination of As (III) in water and soil samples. The results were agreed well with the result obtained from the hydride generation atomic absorption spectrometry.     

Dendritic Silver/Silicon Dioxide Nanocomposite Modified Electrodes for Electrochemical Sensing of Hydrogen Peroxide

A novel biosensor for hydrogen peroxide was prepared by immobilizing horseradish peroxidase (HPR) on newly synthesized dendritic silver/silicon dioxide nanocomposites, which were coated on a glassy carbon electrode. The modified electrode was characterized with XPS, SEM, and electrochemical methods. This biosensor showed a very fast amperometric response to hydrogen peroxide with a linear range from 0.7 to 120 μM, a limit of detection of 0.05 μM and a sensitivity of 1.02 mA mM^?1 cm^?2. The Michaelis‐Menten constant of the immobilized HRP was estimated to be 0.21 mM, indicating a high affinity of the HRP to H₂O₂ without loss of enzymatic activity. The preparation of the proposed biosensor was convenient, and it showed high sensitivity and good stability.     

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.     

Magnetite Nanorods Stabilized by Polyaniline/Reduced Graphene Oxide as a Sensing Platform for Selective and Sensitive Non‐enzymatic Hydrogen Peroxide Detection

In this study, magnetite nanorods stabilized on polyaniline/reduced graphene oxide (Fe₃O₄@PANI/rGO) was synthesized via a wet‐reflux strategy. The possible formation of Fe₃O₄@PANI/rGO was morphologically and structurally verified by field emission scanning electron microscopy (FE‐SEM), Fourier transform infrared (FT‐IR) spectroscopy, Raman spectroscopy, X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). Furthermore, the thermal stability of Fe₃O₄@PANI/rGO was measured by a thermogravimetric analyzer (TGA); the composite had good thermal stability owing to the ceramic nature of Fe₃O₄. The Fe₃O₄@PANI/rGO has been applied as a potential sensing platform for electrochemical detection of hydrogen peroxide (H₂O₂). By the combined efforts of extended active surface area, active carbon support, more catalytic active sites and high electrical conductivity, the Fe₃O₄@PANI/rGO exhibited an improved performance toward the non‐enzymatic detection of H₂O₂ in 0.5 M KOH with a fast response time (5 s), high sensitivity (223.7 μA mM^?1 cm^?2), low limit of detection (4.45 μM) and wide linear range (100 μM–1.5 mM). Furthermore, the fabricated sensor exhibited excellent recovery rates (94.2–104.0 %) during real sample analysis.