Electrochemical Behavior and Voltammetric Determination of Curcumin at Electrochemically Reduced Graphene Oxide Modified Glassy Carbon Electrode

This work presents a sensitive voltammetric method for determination of curcumin by using a electrochemically reduced graphene oxide (ERGO) modified glass carbon electrode (GCE) in 100 mM KCl‐10 mM sodium phosphate buffer solution (pH 7.40). The electrochemical behaviors of curcumin at ERGO/GCE were investigated by cyclic voltammetry, suggesting that the ERGO/GCE exhibits excellent electrocatalytic activity towards curcumin, compared with bare GCE and GO/GCE electrodes. The electrochemical reaction mechanisms of curcumin, demethoxycurcumin and bisdemethoxycurcumin at the ERGO/GCE were also investigated and discussed systematically. Under physiological condition, the modified electrode showed linear voltammetric response from 0.2 μM to 60.0 μM for curcumin, with the detection limit of 0.1 μm. This work demonstrates that the graphene‐modified electrode is a promising strategy for electrochemical determination of biological important phenolic compounds.     

正丁基氯化镁还原氧化石墨烯的表征

采用元素分析、红外光谱(FTIR)、X射线光电子能谱(XPS)、拉曼光谱、X射线衍射(XRD)、固体¹³C核磁共振波谱(¹³C MAS NMR)、热失重分析(TGA)、导电率测试以及原子力显微镜(AFM)等手段对正丁基氯化镁还原的氧化石墨烯进行了系统的表征. 结果表明, 正丁基氯化镁可以有效还原氧化石墨烯, 随着其用量的增加, 氧化石墨烯还原程度增加, 碳/氧摩尔比升高, 片层间距减小, 热稳定性增强, 导电率增大(可达3.6×10² S/m). 还原后部分氧化石墨烯片层发生聚集.     

电还原氧化石墨烯-金纳米棒修饰电极对酒石黄的测定

本文制备了氧化石墨烯-金纳米棒复合物(GO-GNRs).利用滴涂法制备了修饰电极(GO-GNRs/GCE),通过循环伏安法,还原了GO-GNRs复合物中的GO,制得电化学还原的石墨烯-金纳米棒修饰电极(ERGO-GNRs/GCE).研究了酒石黄在不同电极上的电流响应,结果表明,ERGO-GNRs/GCE对酒石黄的氧化有很好的电催化作用,其浓度在0.05～6.0μmol/L范围内与氧化峰电流呈良好的线性关系,检出限为15 nmol/L.利用ERGO-GNRs/GCE可完成样品中酒石黄含量的测定.     

Comparative Studies on Electrocatalytic Activities of Chemically Reduced Graphene Oxide and Electrochemically Reduced Graphene Oxide Noncovalently Functionalized with Poly(methylene blue)

This study compares the electrocatalytic activities of chemically reduced graphene oxide (crGO) and electrochemically reduced graphene oxide (erGO), which are both noncovalently functionalized with a polyaromatic dye, poly(methylene blue) (polyMB), toward the oxidation of β‐nicotinamide adenine dinucleotide (NADH). PolyMB‐crGO and polyMB‐erGO composites were obtained via electropolymerization of methylene blue on crGO and GO modified glassy carbon (GC) electrodes, respectively. Cyclic voltammetry (CV) results indicate that these two types of integrated electrodes reveal different electrocatalytic activities. PolyMB‐crGO integrated electrode possesses lower catalytic oxidation potential, suggesting higher catalytic activity. The present study is helpful for the understanding and screening of graphene‐based advanced carbon nanomaterials for potential electrochemical applications.     

电位调控制备还原氧化石墨烯的电催化性能研究

本文通过控制电位还原氧化石墨烯,可控制备不同含氧官能团的石墨烯纳米材料。以多巴胺、[Fe(CN)_6]~(3-)、NADH为电活性探针,研究了石墨烯表面含氧官能团、缺陷、表面荷电性质以及导电性等对石墨烯电催化性能的影响。研究发现,低还原程度的氧化石墨烯表面含有大量缺陷和丰富的官能团,能够促进多巴胺自催化反应,也有利于K_3[Fe(CN)_6]在电极表面的电子转移;随着氧化石墨烯还原程度提高,其导电性逐渐得到改善,且其表面官能团和缺陷位点数量逐渐减少,对NAD~+的吸附变弱,因而能促进NADH发生电催化氧化。     

Sensitive Voltammetric Determination of Baicalein at Thermally Reduced Graphene Oxide Modified Glassy Carbon Electrode

This work presents a sensitive voltammetric method for determination of the flavonoid baicalein by using a thermally reduced graphene oxide (TRGO) modified glassy carbon electrode (GCE) in 100 mM KCl‐10 mM sodium phosphate buffer solution (pH 7.40). The surface morphology and structure of TRGO investigated by atomic force microscopy, FT‐IR spectroscopy and Raman spectroscopy reveal that the TRGO prepared maintained as single or bilayer sheets and with significant edge‐plane‐like defect sites. The TRGO/GCE modified electrode shows more favorable electron transfer kinetics for potassium ferricyanide and potassium ferrocyanide probe molecules, which are important electroactive compounds, compared with bare GCE and GO/GCE electrodes. The electrochemical behaviors of baicalein at the TRGO/GCE were investigated by cyclic voltammetry, suggesting that the TRGO/GCE exhibits excellent electrocatalytic activity to baicalein. Under physiological conditions, the modified electrode showed linear voltammetric response from 10 nM to 10 µM for baicalein, with a detection limit of 6.0 nM. This work demonstrates that the graphene‐modified electrode is a promising tool for electrochemical determination of flavonoid drugs.     

自由基反应诱导的溴功能化还原氧化石墨烯的制备

以氧化石墨烯(GO)为原料,N-溴代丁二酰亚胺(NBS)为溴代试剂,硫代硫酸钠为还原剂,通过羧基化、溴化和还原三步法,采用自由基反应的方式制备了溴功能化还原氧化石墨烯(rGOBr).通过X射线衍射、扫描电子显微镜、红外光谱、拉曼光谱以及X射线光电子能谱等手段对rGOBr的结构、微观形貌和元素组成进行了表征.结果表明,溴元素以共价键的形式分布在石墨烯表面.本方法原料来源广泛、操作简单且条件温和,为石墨烯的溴功能化提供了一条新途径.     

Determination of Explosives Using Electrochemically Reduced Graphene

A graphene‐based electrochemical sensing platform for sensitive determination of explosive nitroaromatic compounds (NACs) was constructed by means of electrochemical reduction of graphene oxide (GO) on a glassy carbon electrode (GCE). The electrochemically reduced graphene (ER‐GO) adhered strongly onto the GCE surface with a wrinkled morphology that showed a large active surface area. 2,4‐Dinitrotoluene (2,4‐DNT), as a model analyte, was detected by using stripping voltammetry, which gave a low detection limit of 42 nmol L⁻¹ (signal‐to‐noise ratio=3) and a wide linear range from 5.49×10⁻⁷ to 1.1×10⁻⁵ M . Further characterizations by electrochemistry, IR, and Raman spectra confirmed that the greatly improved electrochemical reduction signal of DNT on the ER‐GO‐modified GC electrode could be ascribed to the excellent electrocatalytic activity and high surface‐area‐to‐volume ratio of graphene, and the strong π–π stacking interactions between 2,4‐DNT and the graphene surface. Other explosive nitroaromatic compounds including 1,3‐dinitrobenzene (1,3‐DNB), 2,4,6‐trinitrotoluene (TNT), and 1,3,5‐trinitrobenzene (TNB) could also be detected on the ER‐GO‐modified GC electrode at the nM level. Experimental results showed that electrochemical reduction of GO on the GC electrode was a fast, simple, and controllable method for the construction of a graphene‐modified electrode for sensing NACs and other sensing applications.     

Voltammetric Determination of Folic Acid Using Adsorption of Methylene Blue onto Electrodeposited of Reduced Graphene Oxide Film Modified Glassy Carbon Electrode

This work presents a sensitive voltammetric method for determination of folic acid by adsorbing methylene blue onto electrodeposited reduced graphene oxide film modified glassy carbon electrode (MB/ERGO/GCE) in 100 mM KCl‐10 mM sodium phosphate buffer solution (pH 7.40). The surface morphology of the MB/ERGO/GCE modified electrode was characterized using scanning electron microscopy, displays that both MB and ERGO distributed homogeneously on the surface of GCE. The MB/ERGO/GCE modified electrode shows more favorable electron transfer kinetics for potassium ferricyanide and potassium ferrocyanide probe molecules, which are important electroactive compounds, compared with bare GCE, MB/GCE, and ERGO/GCE. The electrochemical behaviors of folic acid at MB/ERGO/GCE were investigated by cyclic voltammetry, suggesting that the modified electrode exhibited excellent electrocatalytic activity towards folic acid compared with other electrodes. Under physiological condition, the MB/ERGO/GCE modified electrode showed a linear voltammetric response from 4.0 μM to 167 μM for folic acid, and with the detection limit of 0.5 μM (S/N=3). The stability, reproducibility and anti‐interference ability of the modified electrode were examined. The developed method has been successfully applied to determination of FA in tablets with a satisfactory recovery from 96 % to 100 %. The work demonstrated that the electroactive MB adsorbing onto graphene modified electrode showed an enhanced electron transfer property and a high resolution capacity to FA.     

Electrochemically Reduced Graphene Oxide as Screen‐printed Electrode Modifier for Fenamiphos Determination

In this study, electrochemically reduced graphene oxide (ERGO) was used for the preparation of a screen‐printed modified electrode and applied for the voltammetric determination of fenamiphos (FNP) in tomato samples. Graphene oxide (GO) used for sensor construction was prepared according to an improved Hummers method and characterized by XRD, TEM, and FTIR, which confirmed the nanomaterial obtention. The ERGO formation was carried out from the electrodeposition by cyclic voltammetry, at 50 mV s^?1 in the potential range of 0.0 to ?1.5 V, during 50 cycles. ERGO‐SPE was used in the evaluation of the voltammetric behavior of FNP. The ERGO‐SPE proposed presented excellent electrochemical performance towards FNP oxidation, promoting an enhance on the anodic peak current and a decrease of peak potential. Under optimized conditions, it was possible to construct an analytical curve, using square wave voltammetry, with a linear region of 0.25 to 25.0 μM, with calculated limits of detection and quantification of 0.067 and 0.22 μM. From this, it was possible to analyze FNP in fortified tomato samples at three concentration levels, which showed recoveries values varying between 82 and 102 %. The ERGO‐SPE device proved useful in determining FNP, where the effect of the electrodeposition of the GO promoted a significant increase in the employability of the printed electrode.     

Simple and Sensitive Voltammetric Determination of Esculetin Using Electrochemically Reduced Graphene Oxide Modified Electrode

A simple and sensitive voltammetric sensor for esculetin, based on electrochemically reduced graphene oxide film modified glassy carbon electrode, was reported for the quantitative determination of esculetin in the Chinese traditional herbal drug Viola yedoensis Makino. Electrochemical impedance spectroscopy and scanning electron microscopy were employed to study the characteristic of the graphene oxide film. The electrochemical behavior of esculetin on this sensor was investigated in pH 3.0 phosphate buffer solution by cyclic voltammetry. Significant advantages were achieved by the excellent conductivity and the high surface‐to‐volume ratio of electrochemically reduced graphene oxide. A calibration plot of oxidation peak currents versus esculetin concentrations was linear in the range of 4.0 ξ 10^‐8 mol L^‐1 to 5.0 ξ 10^‐6 mol L^‐1 with a detection limit of 2.0 ξ 10^‐8 mol L^‐1. The practical application of the present sensor was demonstrated by determining the concentration of esculetin in real sample with no interference.     

电化学法制备部分还原氧化石墨烯薄膜及其光电性能

提供了一种快速制备氧化石墨烯(GO)薄膜的方法, 并通过调节GO薄膜的含氧量来调控其能级结构.采用阳极电泳及阴极电化学还原联用的方法在F掺杂SnO₂(FTO)导电玻璃上制备出不同层数及含氧量的GO薄膜, 并通过扫描电镜(SEM)、X射线衍射(XRD)、紫外可见(UV-Vis)光谱、X射线光电子能谱(XPS)、拉曼光谱及电化学分析对样品进行表征. 用20-350 s 不同时间电泳沉积得到层数约为77-570层的GO薄膜. 经过不同时间阴极还原的GO薄膜的禁带宽度为1.0-2.7 eV, 其导带位置及费米能级也随之改变. GO作为p型半导体, 与FTO导电膜之间会形成p-n 结, 在光强为100 mW·cm^-2的模拟太阳光照射下, 电泳300 s 且电化学还原120 s时GO薄膜阳极光电流密度达到5.25×10^-8 A·cm^-2.     

Electrical Conductivity of Alkaline-reduced Graphene Oxide

A green route using a very simple and straightforward ultrasonic process under alkaline conditions, rather than a general chemical reduction process using hydrazine, was utilized to obtain the hydrophilic reduced graphene oxide(RGO) sheets, via removing oxygen functional groups from graphene oxide(GO) and repairing the aromatic structure. It is found that the conductivity of the obtained RGO could be tuned by changing pH value in alkaline solution, and the current-voltage(I-V) curves of both GO and RGO are nonlinear and slightly asymmetric. Under the same applied voltage, the current of RGO is much larger than that of GO, indicating a pronounced increase in the electrical conductivity of RGO, compared to that of GO.     

氧化石墨烯的可控还原及结构表征

采用氧化还原法, 通过控制还原时间制备了不同还原程度的石墨烯; 用红外光谱、 紫外光谱、 拉曼光谱、 X射线衍射、 热重分析、 电导率测量等多种手段系统研究了不同还原程度石墨烯的结构与性能; 采用透射电子显微镜、 扫描电子显微镜和原子力显微镜比较了氧化石墨烯和石墨烯的形貌. 结果表明, 随着还原程度的增加, 石墨烯中含氧基团减少, 紫外吸收峰逐渐红移, D带与G带的强度比增加, 热稳定性和导电性提高. 微观结构表征说明石墨烯比氧化石墨烯片的厚度增加, 褶皱增多.     

A Green and Mild Approach of Synthesis of Highly-Conductive Graphene Film by Zn Reduction of Exfoliated Graphite Oxide

We report a simple and green approach to synthesize reduced graphene oxide (RGO) nanosheets at room temperature based on Zn reduction of exfoliated GO. The evolution of GO to RGO has been characterized by X-ray diffraction, UV-Vis absorption spectroscopy and Raman spectroscopy. The results of X-ray photoelectron spectroscopy reveal that the atomic ratio of carbon to oxygen in the RGO can be tuned from 1.67 to 13.7 through controlling the reduction time. Moreover, the conductivity of the RGO is measured to be 26.9±2.2 kS/m, much larger than those previously obtained by chemical reduction through other reducing agents. More importantly, the resistance of the RGO film with 20 nm thick-ness can be as low as 2 kΩ/square, while a high transparency over 70% within a broad spectral range from 0.45 μm to 1.50 μm can be retained. The proposed method is low-cost, eco-friendly and highly-effcient, the as-prepared thinner RGO films are useful in a variety of potential application fields such as optoelectronics, photovoltaics and electrochemistry by serving as an ultralight, flexible and transparent electrode material.     

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.     

氧化石墨烯水热还原前后的发光光谱

分别采用改进Hummers方法和水热还原法制备了氧化石墨烯(GO)和还原氧化石墨烯(RGO)。 GO和RGO经透射电子显微镜(TEM)、紫外-可见吸收光谱(UV-Vis)、红外光谱(IR)、荧光发射和激发光谱(PL、PLE)等技术手段进行了表征。 荧光发射光谱显示,氧化石墨烯(GO)在可见光的激发下可以得到波长在600~800 nm范围内的宽谱近红外荧光。 通过比较氧化石墨烯水热还原前后的光谱变化,发现氧化石墨烯近红外荧光起源于氧化石墨烯的表面含氧基团,如C=O、COOH。 近红外荧光穿透性好、对生物组织损坏小,非常适合于生物成像,预示着氧化石墨烯在生物成像方面的应用潜力。     

Label-Free Fluorescent Aptasensor Based on a Graphene Oxide Self-Assembled Probe for the Determination of Adenosine Triphosphate

A sensitive and selective fluorescent aptasensor for adenosine triphosphate (ATP) was fabricated, composed of unbound SYBR Green I, graphene oxide, and a label-free detection probe. When ATP and complementary DNA of a signal probe were introduced, π-stacking interactions repelled the probe from the graphene oxide and formed a DNA-SYBR Green I duplex structure, triggering an increase in the fluorescence. ATP was determined over a linear range of 10 to 700 nM with a detection limit of 1 nM. The method displayed good selectivity, and is currently the most sensitive ATP fluorescence method. Furthermore, prominent fluorescence signals were also obtained in cellular assays. Consequently, the biosensor may have significant applications in protein, pathogenic microorganisms, and small molecule detection.     

Electrochemical Sensor for Sensitive Determination of Capsaicin Using Pd Decorated Reduced Graphene Oxide

In this work, the reduced graphene oxide functionalized with poly dimethyl diallyl ammonium chloride (PDDA) modified palladium nanoparticles (PDDA‐rGO/Pd) had been facile synthesized and used as the sensing layer for sensitive determination of capsaicin. The prepared composite was characterized by transmission electron microscopy, UV‐visible absorption spectroscopy. The image demonstrated that Pd nanoparticles were uniformly distributed on the graphene surface. The electrochemical properties of the prepared sensor were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results showed that the nanocomposite exhibits attractive electrocatalytic activity towards the oxidation of capsaicin. This attributed to the synergistic action of the excellent properties of Pd nanoparticles and graphene nanosheets. Under optimized conditions, the electrochemical sensor possessed a dynamic linear range from 0.32 μM to 64 μM with a detection limit of 0.10 μM (S/N=3) for capsaicin detection. Moreover, the cost‐effective and simple fabrication procedure, good reproducibility and stability as well as acceptable accuracy for capsaicin determination in actual samples are also the main advantages of this method, which might have broad application in other amide alkaloid detection.     

电还原氧化石墨烯-铁氰化钴修饰电极对肼的测定

本文提出了一种新的水合肼的测定方法。利用静电作用,在氧化石墨烯(GO)表面吸附一层均匀分散的Co2+形成GO-Co2+复合物,通过恒电位法电还原复合物中的GO,再利用循环伏安法将吸附的Co2+转化为铁氰化钴(CoHCF),制得电还原的氧化石墨烯-铁氰化钴修饰玻碳电极(ERGO-CoHCF/GCE)。采用扫描电子显微镜(SEM)对修饰电极表面进行了表征。研究了水合肼在该修饰电极上的电化学行为及在不同电极上的电流响应。结果表明:ERGO-CoHCF/GCE对肼具有很好的电催化氧化作用,其浓度与氧化峰电流呈良好的线性关系。