基于金纳米粒子/Fe-MIL-88-NH2的比率型C反应蛋白免疫传感器

以金纳米粒子(Au nanoparticles, AuNPs)功能化的金属有机骨架材料(Fe-MOFs, Fe-MIL-88-NH₂)为基质材料,构建了双信号比率型免疫传感器,用于C-反应蛋白(C-reactive protein,CRP)的检测。八面体结构的Fe-MOFs不仅提供了较大的有效表面积,可增加固定生物分子的量,促进电子和离子的传输,而且表现出良好的导电性。将AuNPs修饰到Fe-MOFs上可以进一步增加比表面积,以捕获大量抗体以及提高电子转移能力。随CRP浓度的增加,K₃Fe(CN)₆/K₄Fe(CN)₆的氧化峰电流减小,而Fe-MOFs的氧化峰电流相对恒定。采用K₃Fe(CN)₆/K₄Fe(CN)₆响应电流与Fe-MOFs的响应电流比值作为定量测定CRP的响应信号。以K₃Fe(CN)₆/K₄Fe(CN)     

基于金属有机骨架材料的电化学生物传感器在癌症检测中的应用

金属有机骨架(metal-organic frameworks, MOFs)材料因具有稳定的骨架结构、可调的孔尺度和大的比表面积等优良特性,被作为固定生物探针的基体,用于构建电化学生物传感器.电化学生物传感器是一种以电极为信号转换器,通过敏感元件,将肿瘤标志物的高特异性与电化学传感器的高灵敏度相结合的检测装置,在临床癌症筛查方面具有重大应用.本文概述了金属有机骨架复合材料的分类,总结了过去五年基于有机金属骨架材料的电化学生物传感器在检测作为癌症早期诊断指标的各种标志物(如癌症标志物、microRNA和DNA)方面的进展,并对其未来发展进行了展望.     

基于金属有机骨架材料的电化学DNA传感器在分析检测领域的应用进展北大核心CSCD

电化学DNA传感器是基于DNA探针与目标DNA之间碱基互补配对原则构建的传感器,根据识别元件与目标物结合前后信号变化实现目标物的检测,已成为传统检测方法的有效替代方法。而金属有机骨架材料(MOFs)具有比表面积大、孔隙率高、孔径可调和热稳定性强等诸多优点,引起学者的广泛关注,已初步用于电化学DNA传感器的构建,并用于肿瘤标志物、抗生素及重金属等的灵敏、准确检测。为此,综述了电化学DNA传感器的DNA探针固定方法及信号物质,重点介绍了基于MOFs的电化学DNA传感器在分析检测领域的应用进展,并对其未来发展方向进行了展望(引用文献50篇)。     

基于酶辅助的比率型电化学适配体传感器用于前列腺特异性抗原检测

基于核酸外切酶Ⅲ(ExoⅢ)辅助靶标循环策略,构建了比率型电化学适配体传感器,并用于前列腺特异性抗原(PSA)的检测。利用亚甲基蓝(MB)作为内置参考信号,当PSA存在时,发夹探针1(HP1)的适配体序列与PSA特异性结合,引起ExoⅢ的2次切割过程,从而实现2次循环扩增反应,导致电极上更多的MB标记的发夹探针3(MB-HP3)被切割;再加入二茂铁(Fc)标记的DNA链(Fc-DNA)与MB-HP3酶切后的片段进行杂交;最终,Fc的信号(I_Fc)增加,而MB的信号(I_MB)基本保持不变。在最佳条件下,I_Fc/I_MB与PSA浓度的对数值在0.001～100 ng/mL范围内呈良好的线性关系,检出限为0.24 pg/mL。该传感器在临床实际样品检测中具有较好的应用前景。     

基于聚中性红/多壁碳纳米管复合材料的比率型电化学传感器检测雌三醇

基于聚中性红/多壁碳纳米管复合材料构建了检测雌三醇的比率型电化学传感器,利用聚中性红作为内参比电活性探针,雌三醇与聚中性红的氧化峰电流比值作为比率电化学信号,实现了雌三醇的定量检测。聚中性红/多壁碳纳米管复合材料具有良好的电导率和电催化性能,可提高检测灵敏度。实验结果表明,雌三醇在聚中性红/多壁碳纳米管复合材料修饰的玻碳电极上发生双电子和双质子的电化学氧化过程。传感器检测雌三醇的线性范围为0.1～2.0μmol/L,检出限为0.08μmol/L(S/N=3)。此传感器具有灵敏度高、抗干扰能力强及稳定性好等优点,可用于雌三醇药膏、人尿液和湖水样中雌三醇的分析。     

金属有机骨架材料构建环丙沙星电化学传感器的研究

本文通过水热合成法合成了钴-对苯二甲酸金属有机骨架材料Co(BDC),并将其与聚丙烯酸钠(PAAS)混合后修饰到玻碳电极(GCE)表面,制得电化学传感器Co(BDC)-PAAS/GCE,通过循环伏安法和差分脉冲法研究了传感器的响应性能,并用于水产品中环丙沙星(CIP)检测.结果 表明,在碱性条件下,Co(BDC)-PA...     

金属有机骨架材料构建氯霉素电化学传感器的研究

本文通过水热合成法合成了镍-均苯三酸金属有机骨架材料(Ni_3(BTC)_2),并将其与聚丙烯酸钠(PAAS)混合后修饰到玻碳电极(GCE)表面,制得电化学传感器(Ni_3(BTC)_2-PAAS/GCE),用循环伏安法和差分脉冲法研究了传感器的响应性能,并用于水产品中氯霉素(CAP)检测。结果表明,Ni_(3 )(BTC)_2对CAP的还原具有较好的电催化作用。差分脉冲峰电流增加量与CAP浓度在3.1×10~(-9)～1.55×10~(-7)mol·L~(-1)范围内呈线性关系,线性方程为ΔI(μA)=139.72 C_(CAP)+9.9616(R~2=0.9988);在1.55×10~(-7)～9.3×10~(-7) mol·L~(-1)范围内呈线性关系,线性方程ΔI(μA)=33.109 C_(CAP)+26.596(R~2=0.9993),检出限为2.0×10~(-9) mol·L~(-1)。使用该传感器检测实际样品鲤鱼和虾肉中CAP的加标回收率在84.3%～96.6%之间。该传感器制作简单,稳定性、选择性和重复性好,可满足水产品中CAP的快速检测需要。     

基于洋麻秆衍生的三维多孔碳/硫堇比率型抗坏血酸电化学传感器

通过碳化洋麻秆得到三维多孔碳材料(3D-KSC),然后将硫堇(Thi)分子直接组装在其孔壁上,制备了比率型抗坏血酸(AA)电化学传感器。采用扫描电子显微镜和能谱仪等对3D-KSC进行结构表征,发现3D-KSC孔壁表面较光滑,同时还存在一些微孔和缺陷,这些孔隙与缺陷的存在,可使Thi分子牢固地固载到3D-KSC的孔壁上。3D-KSC/Thi修饰电极催化AA的氧化峰出现在0.015 V处,而Thi自身在-0.24 V处的氧化峰不随AA浓度的增加而改变,利用这两个氧化峰的峰电流密度之比设计了一种比率型AA电化学传感器。电化学测试结果表明,3D-KSC/Thi具有导电性能好、电阻值较小、电极与电解液间的离子扩散速率快等特点。3D-KSC/Thi对AA的检测具有良好的选择性、宽的线性范围(18.2μmol/L～8.0 mmol/L)和低的检出限(6.0μmol/L)。用于维生素片中AA含量测定,回收率为100.7%～101.2%,表明此传感器具有潜在的实际应用前景。     

A Novel Electrochemical Sensor Based on Copper‐based Metal‐Organic Framework for the Determination of Dopamine

A glassy carbon electrode (GCE) modified with a copper‐based metal‐organic framework (MOF) [HKUST‐1, HKUST‐1 = Cu₃(BTC)₂ (BTC = 1,3,5‐benzenetricarboxylicacid)] was developed as a highly sensitive and simple electrochemical sensor for the determination of dopamine (DA). The MOF was prepared by a hydrothermal process, and the morphology and crystal phase of the MOF were characterized by scanning electron microscopy (SEM) and X‐ray diffraction (XRD), respectively. Meanwhile, the electrochemical performance was investigated using cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS). Under optimized conditions, the modified electrode showed excellent electrocatalytic activity and high selectivity toward DA. The linear response range was from 5.0 × 10⁻⁷ to 1.0 × 10⁻⁴ M and the detection limit was as low as 1.5 × 10⁻⁷ M. Moreover, the electrochemical sensor was used to detect DA in real samples with excellent results. MOF‐based sensors hold great promise for routine sensing applications in the field of electrochemical sensing.     

基于铜离子与DNA相互作用的铜离子检测

利用铜离子(Cu~(2+))可与DNA分子中的碱基相互作用形成络合物的性质,将Cu~(2+)富集在DNA修饰电极表面,进而采用微分脉冲伏安法(DPV)实现了铜离子的检测.此外,由于乙二胺四乙酸(EDTA)对Cu~(2+)具有更强的络合能力,富集于DNA修饰电极表面的Cu~(2+)很容易被洗脱液中的EDTA络合,从而实现修饰电极的再生和重复利用.实验结果表明,在最佳实验条件下,Cu~(2+)浓度在2.0×10-6~1.0×10-5mol/L和2.0×10-5~1.0×10-4mol/L范围内与其相对还原峰电流强度(I-I0)呈良好的线性关系,且该传感器简单、稳定,可循环使用.     

基于石墨烯修饰的铜离子印迹电化学传感器研制与应用

以铜离子为模板离子,多巴胺为功能单体,采用电聚合法在石墨烯修饰碳电极表面成功制备对铜离子有高选择性和高灵敏性的印迹电化学传感器。采用差分脉冲伏安法和循环伏安法对该印迹传感器的电化学行为进行详细研究。优化检测条件,该印迹电化学传感器的响应电流与铜离子浓度的负对数在5×10_-6~5×10_-11 mol/L的浓度范围内呈良好的线性关系,最低检测限为1.0 × 10_-11mol/L。该印迹电化学传感器成功用于实际水样中的微量铜离子分析。     

基于金属有机框架结构的分子印迹聚合物电化学传感器检测猪尿中苯乙醇胺A

以苯乙醇胺 A ( PEA )为模板分子、对氨基苯硫酚( PATP )为功能单体和有机配体、金纳米颗粒( AuNPs)为金属中心,通过原位电聚合在金电极表面成功制备了具有金属有机框架( MOFs)结构的分子印迹聚合物( MIP)复合膜,构建了具有分子识别特性的复合膜电化学传感器,实现了对PEA的灵敏检测。采用电化学技术和扫描电镜对修饰电极进行表征。优化了扫描速率、pH值、洗脱时间和富集时间等检测条件。在优化条件下,此电化学传感器对PEA在1.0×10-13~1.0×10-9 mol/L范围内有很好的线性关系,相关系数达到0.996,检出限为1.0×10-13 mol/L。在猪尿液中添加不同浓度的PEA,回收率在92.7%~108.4%,相对标准偏差小于8.0%。本方法对实际猪尿中PEA的检测具有很好的灵敏度、特异性和稳定性。     

Impedimetric Detection of DNA Damage with the Sensor Based on Silver Nanoparticles and Neutral Red

Novel electrochemical DNA‐sensor based on glassy carbon electrode (GCE) modified with Ag nanoparticles, Neutral red covalently attached to its surface and native DNA adsorbed on modifier coating was developed for the estimation of DNA damage on example of model system based on Fenton reagent. As was shown, the oxidation process resulted in synchronous increase of electron transfer resistance and capacitance measured by electrochemical impedance spectroscopy (EIS). The contribution of each sensor component on the signal was specified and sensitivity estimated against similar surface coatings. The shift of EIS parameters was found to be higher than that of similar biosensors reported. The DNA sensor was tested on the estimation of antioxidant capacity of green tea infusions again the results of coulometric titration with electrogenerated bromine.     

Electrochemical Detection of DNA Hybridization Based on the Probe Labeled with Carbon‐Nanotubes Loaded with Silver Nanoparticles

A sensitive electrochemical method for the detection of DNA hybridization based on the probe labeled with multiwall carbon‐nanotubes (MWNTs) loaded with silver nanoparticles (Ag‐MWNTs) has been developed. MWNTs were electroless‐plated with a large number of silver nanoparticles to form Ag‐MWNTs. Probe single strand DNA (ss‐DNA) with a thiol group at the 3′‐terminal labeled with Ag‐MWNTs by self‐assembled monolayer (SAM) technique was employed as an electrochemical probe. Target ss‐DNA with a thiol group was immobilized on a gold electrode by SAM technique and then hybridized with the electrochemical probe. Binding events were monitored by differential pulse voltammetric (DPV) signal of silver nanoparticles. The signal difference permitted to distinguish the match of two perfectly complementary DNA strands from the near perfect match where just three base pairs were mismatched. There was a linear relation between the peak current at +120 mV (vs. SCE) and complementary target ss‐DNA concentration over the range from 3.1×10^?14 to 1.0×10^?11 mol/L with a detection limit of 10 fmol/L of complementary target ss‐DNA. The proposed method has been successfully applied to detection of the DNA sequence related to cystic fibrosis. This work demonstrated that the MWNTs loaded with silver nanoparticles offers a great promising approach for sensitive detection of DNA hybridization.     

A Reagentless Electrochemical DNA Sensor Based on a Self-powered DNA Machine

Herein, a reagentless electrochemical DNA sensor based on a self-powered DNA machine for detecting survivin mRNA in cells is developed. The metal-organic framework (MOFs) loaded with DNAzyme cofactors (Mn²⁺) is coated on PTFE rods on the Au surface and assembled with the DNA walker, overcoming the complexity of adding metal ions from the external environment. In addition, the orbital chain is modified by a synthetic bisferrocene signal marker, which further enables signal amplification. Under optimal conditions, the sensor exhibits a range from 1×10⁻¹⁴ mol/L to 1×10⁻⁸ mol/L with a detection limit (S/N=3) of 1.28 fM.     

基于杂交指示剂的无标记适配体电化学传感器用于铅离子检测

为克服传统重金属铅离子(Pb²⁺)检测方法无法适应现场在线分析的缺陷,该研究以杂交指示剂亚甲基蓝(MB)作为电化学信号探针,以适配体作为Pb²⁺识别原件构建无标记适配体电化学传感器。在金电极表面,通过先后修饰适配体及其互补序列cDNA形成双链,随后吸附在双链间的MB通过差分脉冲伏安法产生强烈的电化学信号。当Pb²⁺存在时,适配体特异性捕获Pb²⁺造成双链断开释放MB,从而造成电信号降低,实现对Pb²⁺的定量检测。构建的电化学传感器对Pb²⁺的线性范围为0.1～100 000μg/L,检出限低至33.4 ng/L,对牛奶和湖水样品的加标回收率分别为87.1%～115%和106%～108%,相对标准偏差(RSD)分别为10%～13%和5.0%～9.5%。该方法构建的无标记适配体电化学传感器具有制备简单、成本低廉、灵敏快捷等优点,有望应用于环境及食品工业中Pb²⁺的现场分析。     

A Novel Electrochemical Sensor for Simultaneous Determination of Hydroquinone,Catechol, and Resorcinol Using a Carbon Paste Electrode Modified by Zn-MOF,Nitrogen-doped Graphite,and AuNPs

In this work, the carbon paste electrode was modified with a composite of a metal-organic framework, nitrogen-doped graphite, and gold nanoparticles and used as an electrochemical sensor for dihydroxybenzene isomers. The morphology and characteristics of the modifiers were found by SEM and FT-IR. Electrochemical techniques showed the specific surface of the electrode to be significantly enhanced. The outcome achieved shows that this novel sensor displays an excellent electro-catalytic activity towards the oxidation of these isomers. The sensor was applied to the simultaneous determination of each three isomers using DPV with a linear response in the concentration range of 5–10⁵ nM.