Sensitive Electrochemical Determination of Catechol with a Graphene Modified Carbon Ionic Liquid Electrode

In this paper a graphene (GR) modified carbon ionic liquid electrode (CILE) was fabricated and used as the voltammetric sensor for the sensitive detection of catechol. Due to the specific physicochemical characteristics of GR such as high surface area, excellent conductivity and good electrochemical properties, the modified electrode exhibits rapid response and strong catalytic activity with high stability toward the electrochemical oxidation of catechol. A pair of well‐defined redox peaks appeared with the anodic and the cathodic peak potential located at 225 mV and 133 mV (vs.SCE) in pH 6.5 phosphate buffer solution, respectively. Electrochemical behaviors of catechol on the GR modified CILE were carefully investigated and the electrochemical parameters were calculated with the results of the electrode reaction standard rate constant (k_s) as 1.24 s^?1, the charge transfer coefficient (α) as 0.4 and the electron transfer number (n) as 2. Under the selected conditions the differential pulse voltammetric peak current increased linearly with the catechol concentrations in the range from 1.0 × 10^‐7 to 7.0 × 10^?4mol L‐1 with the detection limit as 3.0 × 10^?8mol L‐1 (3σ). The proposed method was further applied to the synthetic waste water samples determination with satisfactory results     

Electrochemical Detection of Epinephrine Using an L-Glutamic Acid Functionalized Graphene Modified Electrode

The development and application of an L-glutamic acid functionalized graphene nanocomposite, modified glassy carbon electrode are reported for the determination of epinephrine. The properties of the nanocomposite were characterized by scanning electron microscopy, ultraviolet-visible absorption spectroscopy, infrared spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The modified electrode had high sensitivity and strongly catalytic activity for the detection of epinephrine. A linear relationship between the epinephrine concentration and the current response was obtained in the range of 1 × 10^?7 M to 1 × 10^?3 M by differential pulse voltammetry with a limit of detection of 3 × 10^?8 M. The modified electrode was employed to determine epinephrine in urine with satisfactory results.     

Graphene oxide-thionine-Au nanostructure composites: Preparation and applications in non-enzymatic glucose sensing

Herein, we demonstrated a facile strategy for preparing high-loading Au nanoparticles using thionine functionalized graphene oxide as the supporting material. Glassy carbon electrodes modified with the as-obtained nanocomposites showed remarkably electrocatalytic activity towards the oxidation of glucose, leading to an enzymeless glucose sensor with a wide linear range and a lower detection limit of 0.05 μmol/L.     

Highly sensitive and selective detection of biothiols using graphene oxide-based “molecular beacon”-like fluorescent probe

A fluorometric method for quantity analysis of biothiols was developed using a graphene oxide (GO)-based “molecular beacon”-like probe, which consisted of FITC labeled thymine (T)-rich single-stranded DNA (ssDNA), GO and Hg²⁺ ions. The labeled ssDNA containing T–T mismatches would self-hybridize to duplex in the presence of Hg²⁺, which can avoid its adsorption on GO and the fluorescence of this GO-based probe was recovered. The fluorescence of the probe quenched after the addition of biothiols such as glutathione (GSH) and cysteine (Cys) owing to thiol groups can selectively competitive ligation of Hg²⁺ ions with T–T mismatches. In the present work, the GO-based probe was used for the determination of GSH and Cys. Under the optimal conditions, a linear correlation was established between fluorescence intensity ratio I₀/I and the concentration of GSH in the range of 2.0 × 10⁻⁹–5.0 × 10⁻⁷ mol L⁻¹ with a detection limit of 1.0 × 10⁻⁹ mol L⁻¹. The linear range for Cys is from 5.0 × 10⁻⁹ to 4.5 × 10⁻⁷ mol L⁻¹ with a detection limit of 2.0 × 10⁻⁹ mol L⁻¹. The proposed method was applied to the determination of GSH in human serum and cell extract samples with satisfactory results.     

Graphene-based solid-phase extraction combined with flame atomic absorption spectrometry for a sensitive determination of trace amounts of lead in environmental water and vegetable samples

Graphene, a novel class of carbon nanostructures, has great promise for use as sorbent materials because of its ultrahigh specific surface area. A new method using a column packed with graphene as sorbent was developed for the preconcentration of trace amounts of lead (Pb) using dithizone as chelating reagent prior to its determination by flame atomic absorption spectrometry. Some effective parameters on the extraction and complex formation were selected and optimized. Under optimum conditions, the calibration graph was linear in the concentration range of 10.0–600.0 μg L⁻¹ with a detection limit of 0.61 μg L⁻¹. The relative standard deviation for ten replicate measurements of 20.0 and 400.0 μg L⁻¹ of Pb were 3.56 and 3.25%, respectively. Comparative studies showed that graphene is superior to other adsorbents including C18 silica, graphitic carbon, and single- and multi-walled carbon nanotubes for the extraction of Pb. The proposed method was successfully applied in the analysis of environmental water and vegetable samples. Good spiked recoveries over the range of 95.3–100.4% were obtained. This work not only proposes a useful method for sample preconcentration, but also reveals the great potential of graphene as an excellent sorbent material in analytical processes.     

基于离子液体-石墨烯-二茂铁的高灵敏电化学免疫传感器检测CEA

研究了在PBS缓冲介质中,一种检测癌胚抗原的新型免标记免疫电化学传感器的制备,将石墨烯、二茂铁的高效催化及壳聚糖的优良生物相容性和成膜性、离子液体的导电性等优势充分结合构建了电化学免疫传感器。通过循环伏安法及交流阻抗对修饰的电极进行表征,在最优条件下,癌胚抗原的质量浓度在0.2～50.0 ng/mL的范围内与差分脉冲伏安法峰电流呈良好的线性关系,回归方程为Δi=0.38-1.31ρ,相关系数分别为0.9967,检测限为0.06 ng/mL,该传感器可用于人血清样品的测定。     

双氯芬酸钠在石墨烯和室温离子液体复合修饰电极上的电化学行为及其测定

运用循环伏安法研究了双氯芬酸钠(DS)在石墨烯(Gene)和室温离子液体1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF6)复合修饰电极上的电化学行为。DS在该复合电极上于0.65V处有一不可逆氧化峰。在40～200 mV/s范围内,其氧化峰电流与扫描速率平方根(v1/2)呈良好线性关系,表明电极过程是受扩散控制。测定了部分电极过程参数,优化了方波溶出伏安法(SWSV)的实验参数,DS浓度在1.0×10-7～1.0×10-4mol/L范围内与峰电流Ipa呈良好线性关系,检出限为8.0×10-8mol/L(S/N=3),加标回收率为95.7%～101.7%。     

一种有效的制备聚乙二醇修饰氧化石墨烯的方法

为提高氧化石墨烯(GO)的生物相容性从而扩展其在高性能生物材料制备中的应用,采用甲苯-2,4-二异氰酸酯作为桥联剂,制备了四臂星型聚乙二醇修饰氧化石墨烯(GO-TDI-sPEG),该产物在水中仍然可以稳定分散.采用傅里叶红外光谱(FTIR)、拉曼光谱(Raman)、X-射线衍射(XRD)、原子力显微镜(AFM)、透射电子显微镜(TEM)和热重分析(TGA)对接枝产物进行表征.产物在2861 cm-1和1093 cm-1处出现的特征红外吸收表明sPEG已接枝到GO上.产物的Raman光谱中D模与G模信号变弱,且ID/IG值变化不大,说明sPEG改性后的氧化石墨物理结构没有发生变化.XRD曲线上产物衍射峰消失,表明经聚合物修饰后氧化石墨被完全剥离.TGA数据表明原始GO在约160℃开始发生热失重,经修饰后,大约在260℃开始热失重,热稳定性增加了约100℃.由TEM图片可以观察到GO及改性石墨烯产物剥离程度较高,且片上分布有较多聚合物点.且AFM图片显示GO的平均厚度大约为0.85 nm,接上聚合物后部分厚度增加到约1.2 nm.     

石墨烯负载高活性Pd催化剂对乙醇的电催化氧化

以石墨粉为原料, 采用Hummers法液相氧化合成了氧化石墨(GO), 然后用化学一步还原制得石墨烯负载钯催化剂. X射线衍射(XRD)、透射电镜(TEM)表征表明, Pd在石墨烯载体上有较好的分散度, 粒径为3-5 nm. 电化学活性面积(EASA)、循环伏安(CV)、计时电流(CA)和计时电位(CP)等电化学测试表明, 与传统Pd/Vulcan XC-72相比, Pd/石墨烯催化剂对碱性介质中乙醇电催化氧化的催化活性有了很大的提高.     

酞菁铅在石墨烯表面吸附行为的拉曼光谱研究

利用石墨烯增强拉曼散射效应可以获得与石墨烯接触的某些分子的拉曼增强信号, 并且对于不同的分子或振动模, 其拉曼增强因子不同. 根据这一特征, 本工作利用拉曼光谱技术对石墨烯表面上酞菁铅(PbPc)分子Langmuir-Blodgett (LB)膜在退火过程中吸附构型的变化进行了跟踪研究. 发现随着退火温度的升高, 石墨烯表面上PbPc分子的拉曼信号经历了一个先增强后减弱的过程, 在升华温度点附近强度达到最大, 表明PbPc发生了由直立向平躺取向的转变; 同时, 在PbPc分子升华温度点附近, 由于对称性破坏导致散射截面低的振动模出现, 并且该振动模强度随着退火温度的进一步升高而增强, 表明非平面的PbPc分子受石墨烯π-π相互作用的影响而形变加剧, 向平面结构转变; 在更高的退火温度下, 则出现一些不属于PbPc分子的拉曼振动峰, 表明PbPc分子在石墨烯表面由Pb(II)被还原成Pb(0).