水胺硫磷分子印迹传感器的制备与应用

在磷酸盐缓冲溶液(PBS)中,以邻苯二胺(o-PD)和没食子酸(GA)为功能单体,水胺硫磷(ICP)为模板分子,采用电位循环扫描法在玻碳电极(GCE)表面进行电聚合,形成绝缘性的分子印迹膜,通过电化学阻抗谱(EIS)和循环伏安法(CV)对分子印迹膜进行表征.在最佳实验条件下,以铁氰化钾[ K3Fe(CN)6]为探针,用差分脉冲伏安法( DPV)对ICP进行定量分析.该传感器在2.00×10 -7～2.00×10-4 mol/L范围内,传感器的响应信号与ICP的浓度呈良好的线性关系,检测限为6.06×10-s mol/L( S/N=3).将其用于蔬果等实际样品中ICP的测定,回收率为95.6％～104.0％.     

在色氨酸存在下利用多壁碳纳米管糊电极和萘酚介质构成的伏安传感器测定N-乙酰半胱氨酸(英文)

A multiwall carbon nanotube modified electrode prepared by incorporating multiwall carbon nanotubes in the electrode of a sensor and naphthol green as a homogeneous mediator was used as a voltammetric sensor for the determination of N‐actylcysteine(N‐AC) in the presence of trypto-phan(Trp). The voltammograms of differential pulse voltammetry of N‐AC in a mixture with Trp were separated from each other by a potential difference of 200 mV, which allowed the determina-tion of both N‐AC and Trp simultaneously. Under the optimum conditions, the electrocatalytic cur-rents increased linearly with N‐AC concentration in the range of 0.25–400 μmol/L(two linear seg-ments with different slopes). The detection limit for N‐AC was 0.08 μmol/L. The kinetic parameters of the system were determined using electrochemical methods. The method was applied for the determination of N‐AC in drug and urine samples.     

以3,4-二羟基肉桂酸为介质的多壁碳纳米管糊电极用于检测药物和尿液样品中的谷胱甘肽(英文)

A sensitive and selective electrochemical sensor for the determination of glutathione(GSH) was developed using a modified multiwall carbon nanotube paste electrode with 3,4 dihydroxy cinnamic acid as a mediator.This modified electrode showed very high electrocatalytic activity for the anodic oxidation of GSH.Under the optimized conditions,the electrocatalytic peak current showed a linear relationship with GSH concentration in the range of 0.5-400.0 μmol/L with a detection limit of 0.1 μmol/L GSH.The relative standard deviations for seven successive assays of 5.0 and 25.0 μmol/L GSH were 2.2% and 2.7%,respectively.The modified electrode was used for the determination of GSH compounds in real urine samples.     

Voltammetric determination of cysteamine at multiwalled carbon nanotubes paste electrode in the presence of isoproterenol as a mediator

A sensitive electrochemical sensor for the determination of cysteamine(CA) was developed using a modified multiwall carbon nanotube paste electrode(MWCNTPE) with isoproterenol(ISPT) as a mediator.This modified electrode showed very high electrocatalytic activity for the anodic oxidation of CA.Under the optimized conditions,the electrocatalytic peak current showed a linear relationship with CA concentration in the range of 0.3–450.0 mmol/L with a detection limit of 0.09 mmol/L CA.The modified electrode was used for the determination of CA in real samples such as urine and drug samples.     

分子印迹聚合物修饰电化学晶体管检测抗坏血酸分子

以抗坏血酸(AA)为模板分子、邻苯二胺(o-PD)为功能单体,在金电极表面电聚合制备分子印迹聚合物膜(MIP),并以该MIP修饰的电极为栅极制备了具有高选择性、高灵敏度的AA电化学晶体管(OECT)传感器件。应用循环伏安法(CV)、交流阻抗法(EIS)对分子印迹聚合物电极进行一系列的表征与检测。实验结果表明:以pH=5.2,浓度为0.2mol/L HAc-NaAc(体积比2.1∶7.9)的缓冲液为背景溶液,o-PD与AA的物质的量之比为1∶2,以0.5V/s的扫描速率在0~0.8V内扫描20圈,所得分子印迹膜电极性能最佳。应用以该分子印迹修饰电极作为栅极的电化学晶体管检测AA,得到AA浓度的检测限为0.3μmol/L,沟道电流与AA浓度在0.3~3μmol/L(低浓度)与3~100μmol/L(高浓度)这2个范围内成线性关系。     

氯丙嗪分子印迹敏感膜传感器的制备与应用

以氯丙嗪为模板分子,邻氨基酚为功能单体,在金电极表面电聚合制备具有特异性识别孔穴的氯丙嗪分子印迹敏感膜(MIP)。 采用循环伏安法(CV)、差分脉冲伏安法(DPV)等研究了印迹膜的性能、结构和分子印迹效应,并与其结构相似的化合物奋乃静和异丙嗪的选择性响应进行了比较,发现传感器对氯丙嗪具有良好的选择性。 氯丙嗪浓度在6.0×10-7～9.0×10-5 mol/L范围内与峰电流呈线性关系,线性方程为:I(μA)=61.25lg c(μmol/L)+23.47(r=0.9975),根据DL=3δb/s计算检出限为2.0×10-7 mol/L,该传感器具有良好的重复性、再生性和高灵敏度。     

Sensitive and selective molecularly imprinted electrochemical sensor based on multi-walled carbon nanotubes for doxycycline hyclate determination

An electrochemical sensor for doxycycline hyclate(DC)detection with high sensitivity and good selectivity is reported.The sensor was fabricated by electro-polymerization of molecularly imprinted polymers(MIPs)in the presence of DC onto multi-walled carbon nanotubes modified glassy carbon electrode(MWCNTs/GCE).The MWCNTs can significantly increase the current response of the sensor,leading to enhanced sensitivity.The MIPs provide selective recognition sites for DC detection.The experimental parameters,such as the polymer monomer concentration,supporting electrolyte pH,the time for electro-polymerization and the incubation time of the sensor with DC were optimized.Under optimized experimental conditions,the sensor displayed a linear range of 0.05μmol/L-0.5μmol/L towards DC detection,with the detection limit of 1.3×10^-2μmol/L.The sensor was successfully applied for recovery test of DC in human serum samples.     

Detection of dopamine at graphene-ZIF-8 nanocomposite modified electrode

A hybrid graphene-ZIF-8 (G-ZIF-8) nanocomposite modified electrode was prepared in our work. SEM characterization shows that nanocrystals of zeolitic imidazolate frameworks (ZIF-8) were homogeneously well-intergrown on the surface of graphene and thus the graphene sheets were refrained from restacking, which implies the high accessible surface area. The BET results further testifies that G-ZIF-8 composites had a larger surface area than 3D graphene. G-ZIF-8 modified electrode exhibited excellent electroanalytical performance for dopamine. The linear concentration range was from 3.0 μmol/L to 1.0 μmol/L with the detection sensitivity of 0.34 μA/μmol/L and the detection limit of 1.0 μmol/L was obtained. The interference study, electrode stability and reproducibility were carried out. In addition, the prepared sensor was applied to the detection of DA in serum sample with recoveries from 96.8% to 100.7%. It is believable that the structure characteristic of G-ZIF-8 nanocomposite is favorable for using MOFs to fabricate highly sensitive electrochemical sensor.     

在3,4-二羟基肉桂酸介质中以多壁碳纳米管为传感器电催化检测L-半胱氨酸(英文)

A highly sensitive electrochemical sensor was prepared for the determination of L-cysteine using a modified multiwall carbon nanotubes paste electrode in the presence of 3,4-dihydroxycinnamic acid(3,4-DHCA) as a mediator, based on an electrocatalytic process. The results indicate that the electrode is electrocatalytically efficient for the oxidation of L-cysteine in the presence of 3,4-DHCA. The interaction between the mediator and L-cysteine can be used for its sensitive and selective determination. Using chronoamperometry, the catalytic reaction rate constant was calculated to be 2.37 × 102 mol–1 L s–1. The catalytic peak current was linearly dependent on the L-cysteine concentration in the range of 0.4–115 μmol/L. The detection limit obtained by linear sweep voltammetry was 0.25 μmol/L. Finally, the modified electrode was examined as a selective, simple, and precise new electrochemical sensor for the determination of L-cysteine in real samples.     

分子印迹电位型传感器快速检测猪尿液中的克伦特罗

以盐酸克伦特罗为模板分子,采用沉淀聚合法合成了克伦特罗的分子印迹聚合物,并以其为离子载体,制得分子印迹聚合物膜克伦特罗离子选择性电极。在最优实验条件下,电极对克伦特罗阳离子的检出限可达7.0×10-8mol/L,线性范围为1.0×10-7～1.0×10-4mol/L,能斯特斜率为55.7 mV/decade。此电极具有优越的选择性、快速的响应时间以及良好的稳定性;已成功应用于实际猪尿样品中克伦特罗的测定,加标回收率为98%～107%,检测时间小于3 min。     

Electrochemical sensor for Cd2+ and Pb2+ detection based on nano-porous pseudo carbon paste electrode

An electrochemical sensor based on self-made nano-porous pseudo carbon paste electrode (nano-PPCPE) has been successfully developed, and used to detect Cd²⁺ and Pb²⁺. The results showed that the electrodes can quantitatively detect trace Cd²⁺ and Pb²⁺, and with satisfied limit of detection, which has great significance in electrochemical analysis and detection.     

石墨烯/铂纳米粒子杂化膜测定肾上腺素

利用循环伏安法制备了石墨烯/铂纳米粒子杂化膜修饰电极,并利用该修饰电极研究了肾上腺素（EP）的电化学行为,建立了测定肾上腺素的电化学方法。 分别利用扫描电子显微镜（SEM）和循环伏安法对电极表面的形貌和电化学性能进行了表征。 试验优化了修饰电极制备过程中影响电极性能的条件和EP的测定条件。 试验结果表明,石墨烯/铂纳米粒子修饰电极对肾上腺素有明显的电催化作用。 在pH=5.0的柠檬酸 磷酸氢二钠缓冲溶液中,EP的氧化峰电流与其浓度在4.4×10-8~2.2×10-6 mol/L的范围内呈良好的线性关系。 线性方程为ipa(10 μA)=0.0753c(mol/L)+3.7653×10-5,r=0.9989,检出限为2.2×10-9 mol/L（S/N=3）。 修饰电极表具有良好的重现性,可用于实际样品的测定。     

Electrochemical sensor based on f-SWCNT and carboxylic group functionalized PEDOT for the sensitive determination of bisphenol A

A simple,sensitive,and reliable method for the voltammetric determination of bisphenol A(BPA) by using carboxylic group functionalized single-walled carbon nanotubes(f-SWCNT)/carboxylic-functionalized poly(3,4-ethylenedioxythiophene)(PC4) complex modified glassy carbon electrode(GCE) has been successfully developed.The electrochemical behavior of BPA at the surface of the modified electrode is investigated by electrochemical techniques.The cyclic voltammetry results show that the as-prepared electrode exhibits strong catalytic activity toward the oxidation of BPA with a well-defined anodic peak at 0.623 V in PBS(0.1 mol/L,pH 7.0).The surface morphology of the 3D network of composite film is beneficial for the adsorption of analytes.Under the optimized conditions,the oxidation peak current is proportional to BPA concentration in the range between 0.099 and 5.794 μmol/L(R~2 = 0.9989),with a limit of detection of 0.032 μmol/L(S/N = 3).The enhanced performance of the sensor can be attributed to the excellent electrocatalytic property of/-SWCNT and the extraordinary conductivity of PC4.Furthermore,the proposed modified electrode displays high stability and good reproducibility.The good result on the voltammetric determination of BPA also indicates that the asfabricated modified electrode will be a good candidate for the electrochemical determination and analysis of BPA.     

以马来松香丙烯酸乙二醇酯为交联剂的茶碱分子印迹膜电化学传感器的研究

利用分子印迹技术, 以马来松香丙烯酸乙二醇酯为交联剂, 丙烯酸为功能单体研制了测定茶碱的新型电化学传感器. 以自由基热聚合的方式于玻碳电极表面制备茶碱分子印迹聚合物膜. 通过循环伏安法、电化学交流阻抗法及计时电流法研究了传感器对茶碱的响应特性. 结果表明, 在最佳的实验条件下, 传感器的峰电流与茶碱浓度在2.00×10^-7～3.45×10^-4 mol/L 范围内呈现出良好的线性关系(线性相关系数为0.9961), 检出限(S/N＝3)为1.00×10^-7 mol/L;该传感器的选择性高, 稳定性和重现性好, 将此传感器用于茶碱缓释片中茶碱的含量测定, 回收率为95.6%～103.8%.关键词 马来松香丙烯酸乙二醇酯; 茶碱; 分子印迹聚合物; 电化学传感器     

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。     

盐酸吡哆辛在聚对氨基苯磺酸修饰电极上的电化学行为与测定

通过电聚合法制备了聚对氨基苯磺酸(PABSA)修饰玻碳电极(GCE),采用循环伏安法(CV)和差分脉冲伏安法(DPV)研究了盐酸吡哆辛(VB₆)在该修饰电极上的电化学行为。 结果表明,VB₆在该修饰电极上的氧化电流显著增加,为裸电极上的7.5倍。 在pH值3.06.5的醋酸缓冲溶液中,VB₆在PABSA/GCE上的电极反应为吸附控制的一电子两质子的不可逆氧化反应。 在优化条件下,使用DPV对VB₆进行了定量检测,线性范围为0.04100 μmol/L,检出限为0.01 μmol/L,是目前所报道的电化学方法测定VB₆的最低检出限,相对平均偏差为3.1%(n=8)。 采用本方法对维生素B₆片中的VB₆进行检测,回收率为106%~108%。     

Paracetamol Sensor Based on Molecular Imprinting by Photosensitive Polymers

A voltammetric paracetamol sensor based on molecularly imprinted polymeric (MIP) micelles was prepared by direct electrodeposition. The MIP micelles were prepared via macromolecule self‐assembly of an amphiphilic photocrosslinkable copolymer using paracetamol as the template molecule. The resultant molecularly imprinted polymeric micelles swelled with increasing pH, and the disassociation of the micelles occurred at pH above approximately 7.4. A robust MIP film with good solvent resistance was formed on the electrode surface by anodic electrodeposition of the MIP micelles and subsequent photocrosslinking, resulting in the fabrication of a MIP electrochemical sensor for detecting paracetamol. The resultant sensor showed good response and selectivity towards paracetamol. In addition, a wide linear range from 0.01 mmol/L to 8 mmol/L and a low detection limit of 1×10^?6 mol/L for paracetamol detection was demonstrated based on this sensor. The MIP sensor also showed good stability and reversibility which was applied to determine paracetamol commercial tablets.     

Voltammetric Determination of Epinephrine in the Presence of Uric Acid Based on Aminated Graphene and Ag NPs Hybrid Membrane Modified Electrode

A hybrid membrane consisted of aminated graphene and Ag nanoparticles（Ag NPs） was prepared on the surface of glassy carbon electrode（GCE） by cyclic voltammetry（CV） with aminated graphene（GR-NH2） as matrix for immobilizing Ag NPs.The morphology and electrochemical properties of this hybrid membrane were characterized by scanning electron microscopy（SEM） and CV,respectively,and on this membrane,the voltammetric behaviors of epinephrine（EP） were studied in detail.The membrane exhibited excellent eletro-catalytic activities for the redox of EP,and could resolve the electrochemical response of EP and uric acid（UA） into two oxidation peaks.The peak current of EP was linear with its concentration in the ranges of 0.916-18.3 μmol/L and 18.3-184 μmol/L.The detection limit was 2.0 nmol/L（S/N=3）.The proposed modified electrode retained the advantages of easy fabrication,high sensitivity and good repeatability for the determination of EP.     

纳米银/石墨烯修饰电极测定青蒿素

本文建立一种新型的青蒿素传感器。首先,在玻碳电极上滴涂氧化石墨,通过电化学方法将氧化石墨还原为石墨烯,然后,在石墨烯上沉积纳米银得到石墨烯/纳米银修饰电极,它作为检测青蒿素的电化学传感器。用此电极对青蒿素进行测定,并通过循环伏安法、差分脉冲伏安法、交流阻抗法等研究其电化学行为。该修饰电极在测定青蒿素溶液时,表现出较正的还原电位和较大的峰电流等优势;对其实验条件如电解质溶液的p H、应用电势等进行了探查,该电化学传感器在青蒿素溶液浓度范围为1.0×10-8~3.0×10-5mol/L时与其还原峰电流呈现良好的线性关系,最低检出限为1.2×10-9mol/L(S/N=3)。此外,对该传感器的稳定性和重现性等也进行了研究,获得令人满意的结果。     

An oxygen reduction sensor based on a novel type of porous carbon composite membrane electrode

The development of a simple, efficient and sensitive sensor for dissolved oxygen is proposed using a novel type of porous carbon composite membrane/glassy carbon electrode based on the low-cost common filter paper by a simple method. The resulting device exhibited excellent electrocatalytic activities toward the oxygen reduction reaction. Scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and electrochemical measurements demonstrated that the porous morphology and uniformly dispersed Fe₃C nanoparticles of the PCCM play an important role in the oxygen reduction reaction. A linear response range from 2μmol/L up to 110 μmol/L and a detection limit of 1.4 μmol/L was obtained with this sensor. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation, was 3.0%. The successful fabrication of PCCM/GC electrode may promote the development of new porous carbon oxygen reduction reaction material for the oxygen reduction sensor.