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.     

电化学还原氧化石墨烯/纳米金-壳聚糖复合膜修饰玻碳电极对尿酸的灵敏测定

将氧化石墨烯(GO)在玻碳电极(GCE)表面进行直接电化学还原,再组装上纳米金-壳聚糖(AuNPCS)聚阳离子,形成了电化学还原氧化石墨烯/纳米金-壳聚糖(ERGO/AuNP-CS)复合膜修饰的玻碳电极。采用扫描电子显微镜(SEM)表征了不同修饰膜表面的形貌,探讨了其对尿酸(UA)分子的差分脉冲伏安(DPV)行为,发现ERGO/AuNP-CS复合膜对UA分子表现出显著的电催化氧化活性。在0.10 mol/L磷酸盐缓冲溶液(pH=6.5)中,扫速为100 mV/s时,此复合膜修饰电极的DPV响应与UA的浓度在0.05~110μmol/L范围内呈性关系,检测限为12.4 nmol/L(S/N=3)。此修饰电极具有良好的选择性、重现性和稳定性,可应用于人体血清和尿液样品中UA的测定,回收率达到93.8%~104.1%。结果与分光光度法和尿酸酶试剂盒法相符。     

纳米金/Nafion/石墨烯修饰玻碳电极检测对苯二酚的研究

采用一步电化学共还原的方法将纳米金(AuNPs)、Nafion、电化学还原石墨烯(ERGO)修饰到玻碳电极(GCE)表面,制成修饰电极AuNPs/Nafion/ERGO/GCE。以扫描电镜对其进行表征,用循环伏安法和微分脉冲伏安法研究对苯二酚在该修饰电极上的电催化行为。优化了实验参数,对苯二酚在2.0～100μmol/L及100～800μmol/L浓度范围内与其氧化峰电流呈良好的线性关系,检出限为0.3μmol/L。用该修饰电极成功地进行了实际水样中对苯二酚含量的测定。     

电化学还原的氧化石墨烯修饰电极检测L-色氨酸

制备了氧化石墨烯修饰玻碳电极,并运用循环伏安法对氧化石墨烯进行了直接的电化学还原,研究了L-色氨酸在该电化学还原的氧化石墨烯修饰玻碳电极上的电化学行为。结果表明,L-色氨酸在该修饰电极上其氧化峰电流与裸玻碳电极相比增大了7.1倍,且峰电位负移80mV。利用差分脉冲伏安法,在pH=6.5的磷酸盐缓冲溶液中测定L-色氨酸,氧化峰电流与其浓度在0.4～65.0μmol/L范围内呈良好的线性关系,相关系数为0.998,方法检出限为0.2μmol/L。     

CuNi/β-环糊精/还原氧化石墨烯修饰电极电化学检测多巴胺

建立了一种循环伏安法制备CuNi/β-环糊精/还原氧化石墨烯修饰玻碳电极(CuNi/β-CD/ERGO/GCE)的方法。通过多巴胺在该修饰电极上的电化学行为发现,该电化学传感器实现了快速、灵敏的测定多巴胺。该传感器用差分脉冲伏安法(DPV)测定多巴胺时,其电化学响应电流与多巴胺浓度在0.01~20μmol/L之间呈线性关系,检测限为8 nmol/L。该传感器用于尿液样品中的多巴胺检测,回收率在95.6%~107.2%之间。     

布洛芬在石墨烯/DNA/纳米金修饰电极上的电化学行为及测定

利用石墨烯/DNA/纳米金(Gr/DNA/GNPs)修饰电极对布洛芬(IB)的电化学行为进行了研究。分别采用紫外-可见分光光度法和扫描电镜成像技术对Gr/DNA/GNPs复合材料进行了表征。比较了不同修饰电极的检测效果并考察了缓冲体系及修饰量等对测定的影响。实验结果表明,IB在Gr/DNA/GNPs复合材料修饰电极上的电化学信号较为明显,在0.1 mol·L-1PBS缓冲溶液(pH 6.8)中,IB于0.83 V处可观察到1个灵敏的氧化峰。在最佳实验条件下对IB进行检测,其线性范围为7.2×10-7~4.9×10-5mol·L-1,检出限为1.5×10-7mol·L-1。干扰实验和重复实验的结果表明,该修饰电极选择性及重现性良好。用于实际样品的检测,结果满意。     

基于两种复合纳米材料修饰的电极对多巴胺的催化氧化

本文先在Au电极表面自组装硫辛酰胺(T-NH_2),再利用电化学还原的方法将还原氧化石墨烯(ERGO)和纳米金(AuNPs)电沉积到T-NH_2表面,采用循环伏安法考察了电极的电化学性能。实验表明,该修饰电极对多巴胺(DA)具有良好的电催化作用,优化条件下,DA的氧化峰电流与其浓度在6.49×10~(-6)~7.62×10~(-3) mol/L范围内呈良好的线性关系(R=0.996),检出限为2.0×10~(-6) mol/L。     

还原氧化石墨烯-多壁碳纳米管复合膜负载金纳米粒子修饰玻碳电极检测双酚A

以水合肼为还原剂,采用均相还原法制备还原氧化石墨烯-多壁碳纳米管复合材料(rGO-MWCNTs),通过滴涂法将其修饰到玻碳电极(GCE)表面.以此复合材料为载体,采用电化学方法制备了金纳米粒子-还原氧化石墨烯-多壁碳纳米管复合膜修饰电极(AuNPs-rGO-MWCNTs/GCE).通过扫描电镜(SEM)、EDS能谱技术和电化学方法对此电极进行了表征.研究了双酚A在修饰电极上的电化学行为.结果表明,此电极对双酚A的电极过程具有良好的电化学活性,在0.10 mol/L PBS溶液(pH 7.0)中,微分脉冲伏安法测定双酚A的线性范围为5.0 × 10-9~1.0 × 10-7 mol/L和1.0 × 10-7~2.0 × 10-5 mol/L,检出限为1.0 ×10-9 mol/L(S/N=3). 将此电极用于模拟水样和超市购物小票样品中双酚A含量的测定,加标回收率分别为97%~110%和98%~104%.     

纳米金/石墨烯复合膜修饰电极检测异烟肼EI北大核心CSCD

先采用滴涂法制备了石墨烯修饰电极(GR/GCE),然后采用电化学方法将纳米金沉积于石墨烯表面制备了纳米金/石墨烯复合材料修饰电极(Au NPs/GR/GCE)。研究了异烟肼(isoniazid,INZ)在该Au NPs/GR/GCE上的电化学行为。结果表明,异烟肼在该修饰电极上有良好的电化学响应。在优化条件下,线性扫描伏安法测定异烟肼的线性范围为1.0×10-7~1.0×10-4mol/L,检出限为5.0×10-8mol/L(S/N=3)。用该法测定了异烟肼注射液中异烟肼的含量,结果令人满意。     

纳米金修饰玻碳电极对甲醛的电催化氧化

利用电沉积方法制备了纳米金(nano-gold,NG)修饰玻碳电极(GCE)。在碱性介质中该电极对甲醛有较好的催化氧化作用,使甲醛在0.65 V左右出现一个氧化峰,依此测定甲醛的含量。通过实验确定了纳米金的沉积电位和沉积时间,以及纳米金对甲醛的催化氧化所需的底液。该法测定甲醛的线性范围为1~1 000μg/L,检出限为0.3 mg/L。加标回收率为98.5%~101.8%。     

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.     

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%。     

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.     

Octahedral Cuprous Oxide Decorated Flexible Reduced Graphene Oxide Paper for Food Sensing Application

This work presents a simple method to fabricate an octahedral cuprous oxide (Cu₂O) decorated two-dimensional (2D) flexible rGOP electrode with filtration and electrodeposition strategies. The characteristic of the Cu₂O/rGOP electrodes was recorded by SEM, EDX, XPS, XRD, and Raman spectroscopy. The results clearly showed that Cu₂O was successfully electrodeposited on the surface of rGOP by controlling the electrodeposition potential without the introduction of any template or surfactant. The electrochemical characterizations of the Cu₂O/rGOP exhibited high electrocatalytic activity toward the reduction of H₂O₂. The linear detection range for the Cu₂O/rGOP flexible sensor was 5.0 μM to 5.5 mM, with a limit of detection of 1.27 μΜ. Subsequently, the developed flexible rGOP sensor was extended for H₂O₂ detection in milk samples for avoiding milk spoilage_. Such judicial preparation of rGOP as a sensing device will certainly pave the way for various other sensing applications including environmental and biomedical applications.     

Multilayer‐Functionalized Reduced Graphene Oxide Decorated with Gold Nanoparticles as a Designed Nanonanocatalyst for the Selective Oxidation of Cyclohexene by Molecular Oxygen in a Solvent‐Free System

The aerobic oxidation of cyclohexene is of great significance from the viewpoints of both fundamental and industry studies as it can transfer the petrochemical feedstock into valuable chemicals. In this research, gold nanoparticles were synthesized on the multi‐layer functionalized reduced graphene oxide . The surface of reduced graphene oxide (rGO) was modified with hydrophobic and hydrophilic layers to create the rGO with scattered hydrophilic positions. The gold nanoparticles were synthesized and immobilized simultaneously in small hydrophilic micro reactors in a mild condition. Characterization of synthesized nanocatalyst was confirmed with different techniques such as TEM, XRD, FT‐IR, and SEM. TEM images of synthesized catalyst show the gold nanoparticles have diameters less than 5 nm. Designed nanonanocatalyst was investigated for the selective liquid phase oxidation of cyclohexene with molecular oxygen in solvent free condition which after optimized conditions a maximum of 88% conversion and 91% selectivity was obtained.     

Chitosan/Nitrogen Doped Reduced Graphene Oxide Modified Biosensor for Impedimetric Detection of microRNA

The development of a low‐cost and disposable biosensor platform for the sensitive and rapid detection of microRNAs (miRNAs) is of great interest for healthcare, pharmaceuticals, and medical science. We designed an impedimetric biosensing platform using Chitosan (CHIT)/nitrogen doped reduced graphene oxide (NRGO) conductive composite to modify the surface of pencil graphite electrodes (PGE) for the sensitive detection of miRNAs. An initial optimisation protocol involved investigation of the effect of NRGO concentration and miR 660 DNA probe concentration on the response of the modified electrode. After the optimization protocol, the sequence‐selective hybridization between miR 660 DNA probe and its RNA target was evaluated by measuring changes on charge transfer resistance, R_ct values. Moreover, the selectivity of impedimetric biosensor was tested in the presence of non‐complementary miRNA (NC) sequences, such as miR 34a and miR 16. The hybridization process was examined both in phosphate buffer (PBS) and in PBS diluted fetal bovine serum (FBS:PBS) solutions. The biosensor demonstrated a detection limit of 1.72 μg/mL in PBS and 1.65 μg/mL in FBS:PBS diluted solution. Given the easy, quick and disposable attributes, the proposed conductive nanocomposite biosensor platform shows great promise as a low‐cost sensor kit for healthcare monitoring, clinical diagnostics, and biomedical devices.     

Selective and Simultaneous Determination of Dihydroxybenzene Isomers Based on Green Synthesized Gold Nanoparticles Decorated Reduced Graphene Oxide

In the present study, we report the simultaneous electrochemical determination of hydroquinone (HQ), catechol (CC) and resorcinol (RC) at gold nanoparticles (Au‐NPs) decorated reduced graphene oxide (RGO) modified electrode. An enhanced and well defined peak current response with a better peak separation of HQ, CC and RC is observed at RGO/Au‐NPs composite than that of RGO and Au‐NPs modified electrodes. The fabricated modified electrode shows a wide linear response in the concentration range of 3–90 µM, 3–300 µM and 15–150 µM for HQ, CC and RC, respectively. The detection limit of HQ, CC and RC is found as 0.15 µM, 0.12 µM and 0.78 µM, respectively.     

Electrochemical Sensor Based on a Novel Pt−Au Bimetallic Nanoclusters Decorated on Reduced Graphene Oxide for Sensitive Detection of Ofloxacin

Pt−Au nanoclusters decorated on the surface of reduced graphene oxide (rGO/Pt−Au) was facilely prepared by one‐pot electrochemical reduction. The morphology and composition of rGO/Pt−Au composites had been characterized by scanning electron microscopy (SEM) coupled with energy‐dispersive X‐ray spectrometry (EDX), fourier transform‐infrared spectroscopy (FT‐IR) and electrochemical methods. Ofloxacin is a member of synthetic quinolones which has been widely used for the treatment of common diseases in humans and animals. The performance of the rGO/Pt−Au nanocomposite toward the oxidation of ofloxacin was compared with the other similar nanostructures like rGO/Pt and rGO/Au. In the optimized conditions, two linear calibration curves were obtained, from 0.08 to 10 μM and 10 to 100 μM ofloxacin. A detection limit of 0.05 μM ofloxacin was observed at pH 5.7 for the GCE/rGO/Pt−Au. The proposed sensor was successfully applied to determine ofloxacin in tablets and human urine samples and the results were satisfactory.     

基于银纳米粒子/氧化石墨烯复合薄膜制备TNP电化学传感器

利用改进的Hummers法制备了氧化石墨烯(GO), 以葡萄糖为还原剂直接在GO表面沉积银纳米粒子(AgNPs)得到性能稳定的AgNPs/GO纳米复合材料;基于该纳米复合材料修饰电极构建了一种新型的2, 4, 6-三硝基苯酚(TNP)电化学传感器。采用原子力显微镜(AFM)、扫描电镜(SEM)、透射电镜(TEM)、紫外可见光谱(UV-Vis)和交流阻抗(EIS)等多种方法对纳米复合薄膜进行了表征;并研究了TNP在复合薄膜修饰电极上的电化学行为和动力学性质。结果表明, AgNPs/GO对TNP有较强的电催化活性, 在复合薄膜修饰电极出现一灵敏的氧化峰和3个还原峰;利用氧化峰可对TNP进行定量分析。同时整个电极过程明显不可逆, 电极反应受到吸附步骤控制;复合膜电极表面覆盖度为5.617×10^-8 mol·cm^-2, 在所研究电位下的速率常数为9.745×10^-5 cm·s^-1。在pH 6.8的磷酸缓冲液中, 当富集电位为-0.70 V, 富集时间为60 s;TNP氧化峰电流与其浓度在5.0×10^-9~1.0×10^-7 mol·L^-1范围内成良好线性关系, 相关系数为0.995 8, 检出限可达1.0×10^-9 mol·L^-1。所制备的电化学传感器稳定性和选择性较好;用于实际水样中TNP的现场快速检测, 加标回收率在 97.6%~103.9%之间。     

基于银纳米粒子/氧化石墨烯复合薄膜制备TNP电化学传感器

利用改进的Hummers法制备了氧化石墨烯(GO),以葡萄糖为还原剂直接在GO表面沉积银纳米粒子(AgNPs)得到性能稳定的AgNPs/GO纳米复合材料;基于该纳米复合材料修饰电极构建了一种新型的2,4,6-三硝基苯酚(TNP)电化学传感器。采用原子力显微镜(AFM)、扫描电镜(SEM)、透射电镜(TEM)、紫外可见光谱(UV-Vis)和交流阻抗(EIS)等多种方法对纳米复合薄膜进行了表征;并研究了TNP在复合薄膜修饰电极上的电化学行为和动力学性质。结果表明,AgNPs/GO对TNP有较强的电催化活性,在复合薄膜修饰电极出现一灵敏的氧化峰和3个还原峰;利用氧化峰可对TNP进行定量分析。同时整个电极过程明显不可逆,电极反应受到吸附步骤控制;复合膜电极表面覆盖度为5.617×10-8mol.cm-2,在所研究电位下的速率常数为9.745×10-5cm.s-1。在pH 6.8的磷酸缓冲液中,当富集电位为-0.70 V,富集时间为60 s;TNP氧化峰电流与其浓度在5.0×10-9~1.0×10-7mol.L-1范围内成良好线性关系,相关系数为0.995 8,检出限可达1.0×10-9mol.L-1。所制备的电化学传感器稳定性和选择性较好;用于实际水样中TNP的现场快速检测,加标回收率在97.6%~103.9%之间。