以还原氧化石墨烯和纳米二氧化锆为DNA探针固定平台电化学测定转基因玉米中特定基因序列（英文）

草胺膦乙酰转移酶基因(PAT)是一种转基因植物的外源DNA片段。本文以还原氧化石墨烯和纳米二氧化锆(nano ZrO_2)的复合物作为固定DNA探针的平台,建立了一种灵敏地检测PAT基因的方法。首先,氧化石墨烯直接在电极表面进行电化学还原,然后将一层nano ZrO_2涂覆于其表面,利用DNA中的磷酸基团与nano ZrO_2中氧的亲和作用固定DNA探针。通过微分脉冲伏安法检测DNA探针与PAT基因片段的杂交,构建了用于检测PAT基因片段的电化学生物传感器。该传感器具有稳定性好,重复性好的特点,可灵敏地检测转基因玉米中的PAT基因,检测限达2. 0×10~(-15)mol/L。     

靶标介导DNA自组装及催化电流放大的microRNA电化学检测研究

该研究报道了一种靶标介导的DNA自组装及催化信号放大免标记电化学传感器定量检测microRNA-21的分析方法。根据靶标序列,设计一条末端标记巯基且具有茎环结构的捕获探针以及两条与捕获探针和靶标部分互补的DNA单链,通过金-硫键作用将捕获探针固定在金电极表面。当靶标(microRNA-21)存在时,自组装形成一种H结构的DNA复合结构;利用核酸链中磷酸骨架静电吸附电解液中的钌氨离子([Ru(NH₃)₆]³⁺,RuHex)以及DNA电子传递作用产生电化学信号;当无靶标时,不能形成DNA复合结构,电化学信号较弱。进一步利用铁氰根离子([Fe(CN)₆]^3-)能够氧化电化学还原产物([Ru(NH₃)₆]²⁺),产生电化学-化学偶联,从而实现催化电流信号放大。采用电化学阻抗谱确证DNA复合结构的形成,采用计时电量法考察捕获探针密度对电化学信号的影响,并优化探针浓度、比例以及自组装时间,采用差示脉冲伏安法进行定量分析。结果...     

基于氧化石墨烯作为传感平台的DNA电化学阻抗谱传感器制备

制备了一种基于氧化石墨烯作为传感平台的无标记DNA传感器。探针DNA通过π-π堆积作用固定到氧化石墨烯表面,电化学交流阻抗法作为传感表征及检测技术。当传感器识别目标DNA时,由于形成双链结构,双链DNA离开氧化石墨烯表面,进入溶液,使得电化学阻抗值减小。因此,可以利用杂化前后DNA传感器所展现出阻抗值的差异,实现对目标DNA的定量检测。结果表明:目标DNA浓度在1.0×10-8~1.0×10-12mol/L范围内,阻抗值变化与目标DNA浓度的对数呈线性关系,检出限为3.5×10-13mol/L(S/N=3)。此外,传感器能区分互补单碱基错配、完全错配的DNA序列。     

基于羧基化聚吡咯-氯化血红素和点触发链置换反应信号放大的电化学生物传感器检测转基因作物中CaMV35S序列

为适应快速增长的转基因生物(GMOs)安全评价与管理的需求,高效、可靠的转基因检测技术研究与应用的重要性日益凸显。该文采用一步法合成了羧基化聚吡咯(cPPy)与氯化血红素(Hemin)的纳米复合物(cPPy-hemin),并以其为信号标签合成了一种DNA双链结构功能化的纳米信标(DNA-cPPy-hemin)。利用cPPy-hemin增强的模拟酶催化活性,结合点触发链置换反应(TSDR)信号放大策略,制备了一种新型电化学基因传感器用于转基因成分的灵敏检测。通过信号探针(Ps)与模板链(Ts)、辅助链(As)结合形成DNA双链体结构中的-NH2功能化cPPy-hemin,制备Ts/As/Ps-cPPy-hemin双链DNA结构的纳米信标。在目标花椰菜花叶病毒35S启动子(CaMV35S)序列和燃料链(Fs)存在下,TSDR过程释放出的Ps-cPPy-hemin与固定在电化学沉积金纳米粒子修饰GCE表面上巯基化的DNA捕获探针(Cs)相结合,利用cPPy-hemin对H₂O₂的模拟酶催化产生的电信号,可实现对CaMV35S的定量检测。在最优条件下...     

石墨烯修饰玻碳电极用于急性早幼粒细胞白血病PML/RARa融合基因的检测

应利用电化学还原法将固定在玻碳电极表面的氧化石墨还原为石墨烯,然后再利用偶联活化剂将氨基修饰的急性早幼粒细胞白血病（APL）PML／RARα融合基因序列探针固定到石墨烯修饰电极表面,以亚甲基蓝（MB）为电化学杂交指示剂,并由差分脉冲伏安法检测人工合成APL的PML／RARα融合基因.结果表明,石墨烯对MB的检测信号起到了很好的增敏作用,杂交前后MB还原峰电流差值与靶标链DNA浓度在5×10-10~2.5×10-9 mol/L范围内呈线性关系,检出限为8×10-11 mol/L.该方法简单、特异性好,有望用于实际样品的检测.     

石墨烯纳米复合材料在电化学生物传感器中的应用

将石墨烯与其他纳米材料复合,是一种拓展或增强其应用的有效方法。借助不同组分间的协同作用,可以改善石墨烯的电学、化学和电化学性质,拓展和增强石墨烯的电化学效应,为固定氧化还原酶,实现直接电化学提供新型、高效的平台,应用于第三代电化学生物传感器的设计和制备,对葡萄糖、胆固醇、血红蛋白、DNA、H₂O₂、O₂、小生物分子等的检测显示出了优异的灵敏度和选择性。本文综述了基于石墨烯构筑的纳米复合材料在电化学生物传感器中的应用研究,包括石墨烯与贵金属、金属氧化物/半导体纳米粒子、高分子、染料分子、离子液体、生物分子等的纳米复合材料,并对石墨烯材料在电化学领域的发展方向和应用前景进行了展望。     

石墨烯修饰电化学适配体传感器测定双酚A

构建了一种检测双酚A(BPA)的电化学适配体传感器。利用在线电化学方法将氧化石墨烯还原为石墨烯,通过石墨烯与单链DNA之间的相互作用,将BPA适配体单链DNA吸附固定在修饰电极上,制备了BPA电化学适配体传感器。以铁氰化钾-亚铁氰化钾平衡电对为电化学探针,利用电化学循环伏安法和差分脉冲伏安法对BPA传感器的性能进行了研究。结果表明,在最优化实验条件下,传感器对BPA的检测线性范围在1.0×10~(-15)~1.0×10~(-10)mol/L之间,检出限为3.3×10~(-16)mol/L(S/N=3)。     

基于催化发卡自组装和 Ru(NH3)63+ 的核酸光电化学灵敏分析

基于催化发卡自组装反应（CHA）和电活性材料[Ru(NH₃)₆]Cl₃,发展了一种“信号增强”型光电化学生物传感器,实现了核酸的灵敏检测. 首先,采用逐层离子吸附法（SILAR）将CdS 固定于TiO₂/ITO 电极表面. 光电材料CdS 不仅能够将TiO₂ 的吸收范围从紫外光区拓展到可见光区,而且还能提高光电转换效率. 之后,通过Cd-S 键将捕获DNA（C-DNA）固定于CdS/ TiO₂/ITO 电极表面. 与此同时,将Au 结合的发卡DNA 探针1（Au-HP1）,发卡DNA 探针2（HP2）和目标DNA（T-DNA）混合物于溶液中进行CHA 反应,得到大量的Au-HP1:HP2 复合物. 再通过Au-HP1:HP2 复合物与C-DNA 的杂交反应将大量的双链DNA 引入到电极表面. 最后,将电活性物质Ru(NH₃)₆³⁺嵌入DNA 的磷酸骨架中,从而使得光电流大幅度的增强. 该光电生物传感器检测核酸的线性范围为10 fmol·L^-1 到 1500 fmol·L^-1,检测线为6.19 fmol·L^-1,在生物分析、新药筛选以及疾病的早期诊断等方面具有潜在的应用前景.     

脱氧核糖核酸在硬脂酸铝离子膜上固定杂交及BAR基因片段检测

将石墨粉、固体石蜡和硬脂酸按一定比例混合制得表面富含羧基的碳糊电极,然后在电极表面组装荷正电的铝离子膜。在硬脂酸铝离子膜上进行DNA探针的固定和与目标基因的杂交。以亚甲蓝为杂交指示剂,用循环伏安法优化了DNA的固定和杂交条件。应用该电化学生物传感器以微分脉冲伏安法对转基因玉米外源BAR基因片段进行了检测,结果令人满意。     

基于单壁碳纳米管-DNA酶复合结构的电化学生物传感器

结合DNA酶优异的氧化还原催化特性和碳纳米管的电化学特性, 制备了单壁碳纳米管-DNA酶复合材料, 并通过壳聚糖将其固定到玻碳电极表面构建了电化学生物传感界面. 研究了单壁碳纳米管-DNA酶复合结构的氧化还原反应催化特性, 并以此为传感平台构建了葡萄糖氧化酶电化学生物传感器. 结果表明, 单壁碳纳米管-DNA酶复合材料修饰的电极对过氧化氢的响应具有较宽的线性范围(5×10^-6~1×10^-2 mol/L)和良好的检测灵敏度(检出限为1×10^-6 mol/L). 采用制备的葡萄糖氧化酶传感器实现了对葡萄糖的快速灵敏检测.     

Synthesis and Electrochemical Performance of Co3O4/Graphene

Co3O4/reduced graphene oxide composites were synthesized via a simple electrochemical method from graphene oxide and Co（NO3）2·6H2O as raw materials.Co3O4 nanoparticles with sizes of around 30-50 nm were distributed on the surface of graphene nanosheets confirmed by scanning electron microscopy and transmission electron microscopy.Electrochemical properties of Co3O4/graphene composite were tested by cyclic voltammetry,galvanostatic charge-discharge,and electrochemical impedance spectroscopy.The Co3O4/reduced graphene oxide composite was used as the pseudocapacitor electrode in the 2 mol/L NaOH aqueous electrolyte solution.The Co3O4/reduced graphene oxide composite electrode exhibited a specific capacitance of 357 F/g at a current density of 0.5 A/g in a three-electrode system.72％ of capacitance was retained when the current density increased to 3 A/g.The Co3O4/reduced graphene oxide composite prepared electrodes show a high rate capability and excellent long-term stability.After 1000 cycles of charge and discharge,the capacitance is still maintained 87％ at a current density of 1 A/g,indicating that the composite is a oromising alternative electrode material used for supercapacitors.     

Ultrafast room-temperature reduction of graphene oxide by sodium borohydride,sodium molybdate and hydrochloric acid

Since graphene-based materials have shown great potential in many fields,it is important to explore ultrafast and high-efficient methods to synthesize reduced graphene oxide(rGO) using inexpensive reducing agents under mild conditions.Here,we reported a novel method for the ultrafast chemical reduction of graphene oxide(GO) at room temperature using sodium borohydride(NaBH₄),sodium molybdate(Na₂MoO₄) and hydrochloric acid(HCl).The reduction was carried out within 2 min.A series of characterization results revealed that the obtained reduced graphene oxide has higher reduction degree than that synthesized by NaBH₄ alone at high temperature.Moreover,rGO electrode based on the present reducing method exhibited a superior specific capacitance of 139.8 F/g at a current density of1 A/g,indicating that it can be used as electrode materials for supercapacitors.     

Synergistic effects of nano-ZnO/multi-walled carbon nanotubes/chitosan nanocomposite membrane for the sensitive detection of sequence-specific of PAT gene and PCR amplification of NOS gene

The remarkable synergistic effects of the zinc oxide (ZnO) nanoparticles and multi-walled carbon nanotubes (MWNTs) were developed for the ssDNA probe immobilization and fabrication of the electrochemical DNA biosensor. The ZnO/MWNTs/chitosan nanocomposite membrane-modified glassy carbon electrode (ZnO/MWNTs/CHIT/GCE) was fabricated and the ssDNA probes were immobilized on the modified electrode surface. The preparation method is quite simple and inexpensive. The hybridization events were monitored by differential pulse voltammetry (DPV) using methylene blue (MB) as an indicator. As compared with previous MWNTs-based DNA biosensors, this composite matrix combined the attractive biocompatibility of ZnO nanoparticles with the excellent electron-transfer ability of MWNTs and fine membrane-forming ability of CHIT increased the DNA attachment quantity and complementary DNA detection sensitivity. The approach described here can effectively discriminate complementary DNA sequence, noncomplementary sequence, single-base mismatched sequence and double-base mismatched sequence related to phosphinothricin acetyltransferase (PAT) gene in transgenic corn. Under optimal conditions, the dynamic detection range of the sensor to PAT gene complementary target sequence was from 1.0 × 10⁻¹¹ to 1.0 × 10⁻⁶ mol/L with the detection limit of 2.8 × 10⁻¹² mol/L. The polymerase chain reaction (PCR) amplification of nopaline synthase (NOS) gene from the real sample of one kind of transgenic soybeans was also satisfactorily detected with this electrochemical DNA biosensor, suggesting that the ZnO/MWNTs/CHIT nanocomposite hold great promises for sensitive electrochemical biosensor applications.     

氢氧化镍纳米线/三维石墨烯复合材料的制备及其电化学性能

采用水热法制备了氢氧化镍纳米线/三维石墨烯复合材料及作为比较的三维石墨烯、氢氧化镍纳米线、还原氧化石墨烯和氢氧化镍纳米线/还原氧化石墨烯, 通过X射线衍射、扫描电镜、热失重分析和氮气吸脱附表征了材料的形貌、结构和组成, 并采用循环伏安法和恒电流充放电测试了复合材料的电化学性能. 结果表明: 氢氧化镍纳米线/三维石墨烯复合材料中直径为20-30 nm的氢氧化镍纳米线和三维结构的石墨烯紧密结合, 相互交联形成网状结构, 其比表面积达到136 m²·g^-1, 孔径分布20-50 nm, 氢氧化镍纳米线的含量达到88% (w,质量分数). 在6 mol·L^-1的KOH电解液中, 复合材料的比电容在1 A·g^-1电流密度下达到1664 F·g^-1, 在1 A·g^-1电流密度下循环3000 次后的比电容保持率为93%. 将复合材料的比电容和循环性能与氢氧化镍纳米线、氢氧化镍纳米线/还原氧化石墨烯、三维石墨烯和还原氧化石墨烯的性能进行比较, 发现三维石墨烯较还原氧化石墨烯具有更高的比表面积和三维多孔结构, 可以更大地提高活性物质的利用率, 进而提高复合材料的比电容和稳定性.     

Electrochemical sensing of DNA immobilization and hybridization based on carbon nanotubes/nano zinc oxide/chitosan composite film

A novel electrochemical DNA biosensor based on zinc oxide （ZnO） nanoparticles and multi-walled carbon nanotubes （MWNTs） for DNA immobilization and enhanced hybridization detection is presented. The MWNTs/nano ZnO/chitosan composite film modified glassy carbon electrode （MWNTs/ZnO/CHIT/GCE） was fabricated and DNA probes were immobilized on the electrode surface. The hybridization events were monitored by differential pulse voltammetry （DPV） using methylene blue （MB） as an indicator. The sensor can effectively discriminate different DNA sequences related to PAT gene in the transgenic corn, with a detection limit of 2.8× 10^-12 mol/L of target sequence.     

A PDDA/poly(2,6-pyridinedicarboxylic acid)-CNTs composite film DNA electrochemical sensor and its application for the detection of specific sequences related to PAT gene and NOS gene

2,6-Pyridinedicarboxylic acid (PDC) was electropolymerized on the glassy carbon electrode (GCE) surface combined with carboxylic group-functionalized single-walled carbon nanotubes (SWNTs) by cyclic voltammetry (CV) to form PDC-SWNTs composite film, which was rich in negatively charged carboxylic group. Then, poly(diallyldimethyl ammonium chloride) (PDDA), a linear cationic polyelectrolyte, was electrostatically adsorbed on the PDC-SWNTs/GCE surface. DNA probes with negatively charged phosphate group at the 5' end were immobilized on the PDDA/PDC-SWNTs/GCE due to the strong electrostatic attraction between PDDA and phosphate group of DNA. It has been found that modification of the electrode with PDC-SWNTs film has enhanced the effective electrode surface area and electron-transfer ability, in addition to providing negatively charged groups for the electrostatic assembly of cationic polyelectrolyte. PDDA plays a key role in the attachment of DNA probes to the PDC-SWNTs composite film and acts as a bridge to connect DNA with PDC-SWNTs film. The cathodic peak current of methylene blue (MB), an electroactive label, decreased obviously after the hybridization of DNA probe (ssDNA) with the complementary DNA (cDNA). This peak current change was used to monitor the recognition of the specific sequences related to PAT gene in the transgenic corn and the polymerase chain reaction (PCR) amplification of NOS gene from the sample of transgenic soybean with satisfactory results. Under optimal conditions, the dynamic detection range of the sensor to PAT gene target sequence was from 1.0x10(-11) to 1.0x10(-6) mol/L with the detection limit of 2.6x10(-12) mol/L.     

功能化石墨烯/活性炭复合电极及不对称电容器脱盐

以3-氨丙基三乙氧基硅烷(AMPTS)修饰氧化石墨(GO)还原合成氨基功能化石墨烯(GP-NH2).傅里叶变换红外(FTIR)光谱和X射线能谱(EDX)分析证明了氨基基团的成功接枝.以GP-NH2为添加剂,制备胺化石墨烯/活性炭(GP-NH2/AC)复合电极,并以GP-NH2/AC为正极,AC电极为对电极,组装不对称电容器(AC||GPNH2/AC)用于电容脱盐.实验表明,AC||GP-NH2/AC单循环脱盐量为7.63 mg·g-1,电流效率达77.6%.利用磺酸重氮盐接枝石墨烯制备磺化石墨烯(GP-SO3H)及磺化石墨烯/活性炭(GP-SO3H/AC)复合电极.并以GPSO3H/AC为负极,GP-NH2/AC为正极,组装不对称电容器(GP-SO3H/AC||GP-NH2/AC)用于电容脱盐,其平均脱盐速率可达0.99 mg·g-1·min-1,比纯AC电极提高了接近5倍.充放电速率提高了30%;而且由于正、负极表面固有电荷的存在,大大降低了反离子效应,电流效率由40%(纯AC||AC对称电容器)提高到92.8%.表明电极内功能化导电石墨烯的存在既提高了导电性,又兼具离子选择性的作用,从而明显改善电极的脱盐性能.     

A Novel Electrochemical Sensor Based on Reduced Graphene Oxide–TiO2 Nanocomposites with High Selectivity for the Determination of Hydroxychloroquine

Russian Journal of Electrochemistry - A simply sensitive sensor based on a reduced graphene oxide–TiO2 nanocomposite modified glassy carbon electrode (RGO–TiO2/GCE) was developed for...     

静电自组装方法合成的具有多孔三维网络结构的Fe_3O_4/石墨烯复合材料作为高性能锂离子电池负极材料(英文)

采用静电自组装方法,分两步合成Fe(OH)3/GO前驱体(GO:氧化石墨烯),再通过水热反应和600°C高纯氮气气氛下煅烧,获得了Fe3O4/石墨烯复合材料.通过X射线衍射(XRD)、扫描电镜(SEM)、高分辨透射电镜(HRTEM)、拉曼(Raman)光谱等多种分析,发现该复合材料具有三维多孔石墨烯网络结构.把合成的这种Fe3O4/石墨烯复合材料作为锂离子电池负极材料,电化学测试结果表明其具有优良的电化学性能:首次放电容量为1390 mAh·g-1,50次循环后容量为819 mAh·g-1.通过对比实验表明,三维石墨烯网络结构的形成对复合材料的电化学循环稳定性起着关键作用.     

Electrochemical Study and Application on Shikonin at Poly(diallyldimethylammonium chloride) Functionalized Graphene Sheets Modified Glass Carbon Electrode

The electrochemical behaviors of shikonin at a poly(diallyldimethylammonium chloride) functionalized graphene sheets modified glass carbon electrode(PDDA-GS/GCE) have been investigated. Shikonin could exhibit a pair of well-defined redox peaks at the PDDA-GS/GCE located at 0.681 V(E_pa) and 0.662 V(E_pc)[vs. saturated calomel electrode(SCE)] in 0.1 mol/L phosphate buffer solution(pH=2.0) with a peak-to-peak separation of about 20 mV, revealing a fast electron-transfer process. Moreover, the current response was remarkably increased at PDDA-GS/GCE compared with that at the bare GCE. The electrochemical behaviors of shikonin at the modified electrode were investigated. And the results indicate that the reaction involves the transfer of two electrons, accompanied by two protons and the electrochemical process is a diffusional-controlled electrode process. The electrochemical parameters of shikonin at the modified electrode, the electron-transfer coefficient(α), the electron-transfer number(n) and the electrode reaction rate constant(k_s) were calculated to be as 0.53, 2.18 and 3.6 s^-1, respectively. Under the optimal conditions, the peak current of differential pulse voltammetry(DPV) increased linearly with the shikonin concentration in a range from 9.472×10^-8 mol/L to 3.789×10^-6 mol/L with a detection limit of 3.157×10^-8 mol/L. The linear regression equation was I_p=0.7366c+0.7855(R=0.9978; I_p: 10^-7 A, c: 10^-8 mol/L). In addition, the modified glass carbon electrode also exhibited good stability, selectivity and acceptable reproducibility that could be used for the sensitive, simple and rapid determination of shikonin in real samples. Therefore, the present work offers a new way to broaden the analytical application of graphene in pharmaceutical analysis.