多壁碳纳米管和分子印迹膜修饰电极检测猪尿液中莱克多巴胺

采用原位热聚合技术,分别以多壁碳纳米管(MWCNs)和分子印迹膜(MIM)修饰丝网印刷电极(SPE),与多壁碳纳米管和非分子印迹膜(NIM)修饰的丝网印刷电极组合在一起,并将其组合的丝网印刷电极通过电极插口与便携式电导仪相连接,组装成检测莱克多巴胺残留的电导型传感器,优化检测条件,并建立了检测莱克多巴胺的标准曲线,测试了实际猪尿样中莱克多巴胺的含量.通过扫描电镜分析了该分子印迹膜的表征结构.结果表明,在莱克多巴胺分子印迹膜表面形成了大量印迹微孔.本传感器装置检测莱克多巴胺具有很高的灵敏度和特异性,检出限为0.033 mg/L,线性范围为0.33～8.0 mg/L,基于猪尿样的检测回收率达到91％～98％,可实现现场快速检测.     

Purification of 3-indolylacetic acid by solid phase extraction

This paper deals with the use of solid-phase extraction (SPE) for the extraction and purification of 3-indolylacetic acid (IAA), the main and most important representative of the plant growth regulators auxins. The procedure is based on the use of C18-SPE columns in two steps. In the first one, raw extract in methanol:water (4:1) is applied on the column in order to remove neutral ballast. In the second step the eluate is diluted with water to a final methanol concentration of 20% (to decrease the elution strength of the solvent) and acidified with formic acid to a final concentration of 1% (to convert the IAA from the anionic to the neutral form). Neutral IAA is then retained on the second SPE column, eluted by (acidified) methanol, and subjected to final analysis. Scintillation counting of tritium labeled IAA standard was used for the investigation and optimization of the SPE procedure. Gas chromatography with mass spectrometric detection was suggested as a convenient method for routine determination of IAA after its methylation with diazomethane. Overall recovery of the procedure was estimated as 89-94% and a physiological level of IAA equal to 0.48 nmol/g (84 ng/g) fresh weight was found using an optimized SPE-GC-MS method.     

基于金属纳米粒子增敏的SPR生物传感器检测吲哚乙酸

本实验建立了表面等离子体共振(SPR)生物传感器检测3-吲哚乙酸(IAA)的方法。制备了两种SPR生物传感器检测IAA:传统模式的SPR生物传感器1和Au/Ag合金纳米粒子增敏的SPR生物传感器2。结果发现:传感器1在IAA浓度范围为175~350μg/L时,浓度与其波数位移值呈线性关系,检出限为25μg/L(S/N=3);传感器2在IAA浓度范围为17.5~250μg/L时,浓度与其波数位移值呈线性关系,检出限为2.2μg/L(S/N=3)。说明基于Au/Ag合金纳米粒子的传感器2比传感器1有较高的灵敏度和较低的检出限。加标回收实验测得加标回收率范围为96%~100.2%,平均值为98.4%。本实验制备的SPR生物传感器具有较好的精密度、稳定性、重现性和特异性。     

Reduced Graphene Oxide/Carbon Nanotube/Gold Nanoparticles Nanocomposite Functionalized Screen‐Printed Electrode for Sensitive Electrochemical Detection of Endocrine Disruptor Bisphenol A

We fabricated a highly sensitive electrochemical sensor for the determination of bisphenol A (BPA) in aqueous solution by using reduced graphene oxide (RGO), carbon nanotubes (CNT), and gold nanoparticles (AuNPs)‐modified screen‐printed electrode (SPE). GO/CNT nanocomposite was directly reduced to RGO/CNT on SPE at room temperature. AuNPs were then electrochemically deposited in situ on RGO/CNT‐modified SPE. Under optimized conditions, differential pulse voltammetry (DPV) produced linear current responses for BPA concentrations of 1.45 to 20 and 20 to 1,490 nM, with a calculated detection limit of an ultralow 800 pM. The sensor response was unaffected by the presence of interferents such as phenol, p‐nitrophenol, pyrocatechol, 2,4‐dinitrophenol, and hydroquinone.     

Stripping Analysis of As(III) by Means of Screen‐Printed Electrodes Modified with Gold Nanoparticles and Carbon Black Nanocomposite

A novel sensor based on carbon black‐gold nanoparticle nanocomposite modified screen‐printed electrode (CB‐AuNPs/SPE) for the detection of As(III) has been developed. The sensor was prepared modifying the SPE with CB and AuNPs by a drop casting automatable deposition. The As(III) was detected by CB‐AuNPs/SPE using anodic stripping voltammetry, with a high sensitivity (673±6 µA µM^?1 cm^?2) and reaching a LOD of 0.4 ppb. Finally, CB‐AuNPs/SPE has been applied to As(III) trace analysis in drinking water, obtaining satisfactory recovery values (99±9 %).     

基于丝网印刷电极的甲胎蛋白电化学免疫传感器

报道了一种基于金纳米粒子(AuNPs)双重信号放大的高灵敏电化学免疫传感器,并应用于肝癌标志物甲胎蛋白(AFP)的检测。通过在丝网印刷电极(SPE)表面电沉积AuNPs提高电极的重现性,利用AuNPs的吸附作用固定AFP抗体,用于捕获样品中的待测AFP抗原,并进一步与固定了辣根过氧化物酶(HRP)标记检测抗体的纳米金免疫探针发生特异性结合,所形成的夹心免疫复合物可以催化底物得到响应电流。用扫描电镜(SEM)和微分脉冲伏安法(DPV)等技术研究电极组装过程以及电极的化学性质,讨论了影响免疫传感器性能的因素。在最优实验条件下,传感器的峰电流信号与AFP浓度在2.5~30ng/mL范围内呈良好的线性关系,检出限为0.16ng/mL。该传感器具有灵敏度高、成本低、仪器体积小的优点,具有较好的应用前景。     

Real‐Time Monitoring of Auxin Vesicular Exocytotic Efflux from Single Plant Protoplasts by Amperometry at Microelectrodes Decorated with Nanowires

Recent biochemical results suggest that auxin (IAA) efflux is mediated by a vesicular cycling mechanism, but no direct detection of vesicular IAA release from single plant cells in real‐time has been possible up to now. A TiC@C/Pt‐QANFA micro‐electrochemical sensor has been developed with high sensitivity in detection of IAA, and it allows real‐time monitoring and quantification of the quantal release of auxin from single plant protoplast by exocytosis.     

One‐step Electrodeposition of Tris(hydroxymethyl) Aminomethane – Prussian Blue on Screen‐printed Electrode for Highly Efficient Detection of Glycosylated Hemoglobin

In this work, the modified Prussian blue (PB) film showed more stable performance in alkaline solution by one‐step electrodepositon of PB with tris(hydroxymethyl) aminomethane (Tris) on screen‐printed electrode (SPE). The morphology and structure of the modified Tris‐PB/SPE was characterized by scanning electronic microscopy, infra spectroscopy, Raman spectroscopy and X‐ray diffraction. It was inferred that the Tris particles embedded in the PB deposit layer resulted in the change of PB structure and improve its stability in alkaline solution. And then, the modified Tris‐PB/SPE was applied in the detection of Glycosylated hemoglobin (HbA1c). The optimum experimental conditions are pH 7.5, 100 mV/s, 4 μL FAOD and 5 min reaction time. The linearship of HbA1c is i=22.90 C+101.9 in the range of 0.1–2 mmol/L. Comparing with PB/SPE, Tris‐PB/SPE shows better sensitivity and recovery.     

The amperometric determination of indole-3-acetic acid based on CeCl<Subscript>3</Subscript>-DHP film modified gold electrode

An amperometric sensor for the determination of indole-3-acetic acid (IAA) based on the CeCl₃-DHP film modified gold electrode was developed. CeCl₃ was dissolved into water in the presence of dihexadecyl hydrogen phosphate (DHP). The IAA sensor was prepared via evaporating solvent of the CeCl₃-DHP dispersion on the gold electrode surface. The amperometric response of IAA on the CeCl₃-DHP film modified gold electrode was investigated. The experimental results indicate that the passivation of the electrode due to the adsorption of the oxidation product of IAA decreases significantly at the CeCl₃-DHP film modified gold electrode, in contrast to that at the bare and the DHP modified gold electrode. The experimental parameters were optimized and an electrochemical method for the determination of IAA was established. The oxidation peak current is linearly with the concentration of IAA from 1 × 10⁻⁷ to 2 × 10⁻⁵ mol l⁻¹ and the detection limit is 3 × 10⁻⁸ mol l⁻¹. The relative standard deviation of eight measurements is 3.2% for 5 × 10⁻⁷ mol l⁻¹ IAA. The IAA in plant leaves were extracted and determined by the IAA sensor.     

Capillary enzyme immunoassay with electrochemical detection for determining indole-3-acetic acid in tomato embryos

An amperometric immunoassay for indole-3-acetic acid (IAA) in tomato embryos was developed. The antibody against IAA was covalently bound to the chemically modified inner surface of a 22 μL silica capillary. The competitive binding of methylated IAA and an IAA alkaline phosphatase conjugate for a limited amount of antibody was accomplished in the silica capillary in 20 min. The enzymatic product p-aminophenol, produced from p-aminophenyl phosphate, was determined by flow injection analysis with amperometric detection. A detection limit for IAA of 3 pg/μL was obtained. The average concentration of IAA in mature embryos measured by this method is 0.37 ± 0.03 μg/g. Although isotope dilution GC-SIM-MS can achieve the same detection limit, the sample analysis is not feasible in such a complicated matrix and further purification and separation are required.     

On-Line Monitoring 1H-Indole-3-Acetic Acid in Plant Tissues Using Molecular Imprinting Monolayer Techniques on a Surface Plasmon Resonance Sensor

A surface plasmon resonance (SPR)-based detection methodology, which allows the identification and quantification of the plant hormone, ¹H-indole-3-acetic acid (IAA) in Peach, Rosa flower, and Crape myrtle bud is described. To achieve high selectivity, a molecularly imprinted monolayer (MIM) was prepared from alkanethiols self-assembled on an SPR sensor chip with preadsorbed template (IAA). The association constant of the MIM to IAA was calculated to be 2.8 × 10¹¹ M^?1 by analysis of the SPR wavenumber changes induced by different concentrations of IAA. A good calibration curve was obtained in a low concentration range of IAA. Moreover, the MIM revealed impressive selectivity with the selectivity factors of 1.0, 0.12, and 0.20 for IAA and other related analogues. Compared to the MIM sensor chip, the affinity of the self-assembled monolayer (SAM) control sensor chip for IAA was significantly low. The single SPR sensor decorated with the MIM was used to determine IAA concentrations in peach, Rosa flower, and Crape myrtle bud, and satisfactory results were obtained. Based on a signal to noise ratio of 3, the detection limits were 0.23 pM for Crape myrtle, 0.20 pM for Peach, and 0.32 pM for Rosa. The method showed good recoveries and precision, 95.7% (RSD 0.54%) for Peach, 98.1% (RSD 3.4%) for Rosa, and 98.1% (RSD 2.5%) for Crape myrtle, spiked with 0.4171 µg, respectively. These results indicate that a combination of SPR sensing and the MIM provides a simple, promising alternative method for determining endogenous IAA in plant tissue in a real-time manner.     

Electrochemical Detection of Epinephrine Based on a Screen-printed Electrode Modified with NiO−ERGO Nanocomposite Film

This study presents a new electrochemical sensor (NiO−ERGO/SPE) for sensitive and selective detection of epinephrine (EPI) on the screen-printed electrode (SPE) which is modified with a nanocomposite film consisting of electrochemically reduced graphene oxide and NiO nanoparticles. After surface functionalization, structural and electrochemical characterization of NiO−ERGO film, DPV signals of NiO−ERGO/SPE towards the oxidation of EPI exhibited a linear correlation in the concentration range of 0.025 μM to 175 μM with a detection limit of 0.015 μM, which reveals NiO−ERGO film is manifested a good electrocatalytic activity for EPI detection compared with the previous reports. The selectivity of NiO−ERGO film was also tested on a very wide scale of possible interferents (ascorbic acid, uric acid, dopamine, lactic acid, phenylalanine, tyrosine, tryptophan, Li⁺, Na⁺, K⁺, Ca²⁺, and Zn²⁺). Moreover, to evaluate the applicability of the proposed sensor for real sample analysis, NiO−ERGO/SPE was successfully utilized for the determination of EPI in pharmaceutical samples.     

梯度洗脱高效液相色谱法测定红花玉兰中4种植物激素

建立了梯度洗脱高效液相色谱法测定红花玉兰中赤霉素(GA3)、生长素(IAA)、脱落酸(ABA)和玉米素(ZT)等4种植物激素的方法。采用Agilent ZORBAX SB-C18柱和紫外检测器,以甲醇和0.1 mol/L乙酸作为流动相进行梯度洗脱,流速1 mL/min,进样量10μL。GA3,IAA和ABA的检测波长为254 nm,柱温35℃;ZT的检测波长为270 nm,柱温40℃。采用外标法进行定量测定,4种植物激素的相关系数均大于0.9990。4种激素的回收率为98.1%~125.2%,相对标准偏差为0.31%~0.92%,日内和日间精密度RSD均<10%。方法可适用于红花玉兰多种组织的植物激素测定,为红花玉兰生长发育特性的研究奠定了基础。     

Nickel/Copper Bilayer‐modified Screen Printed Electrode for Glucose Determination in Flow Injection Analysis

This work reports about the performance of a Ni/Cu‐modified screen printed electrodes (SPE/Ni/Cu), prepared by physical vapor deposition (PVD) in an oblique angle configuration (OAD), for non‐enzymatic glucose sensing applications. SPE/Ni/Cu electrodes showed an excellent reversibility and a catalytic behavior for detection of glucose that were controlled by the diffusion of reactants up to the active sites at the electrode surface. The study with a flow injection analysis (FIA) setup of the main experimental variables affecting the detection process has shown that the developed electrode system had an excellent glucose sensitivity of 1.04 A M⁻¹cm⁻² (R²:0.999), a linear response up to 1 mM, a limit of detection of 0.33 μM and a time of analysis of ca. 30 s per sample. The selectivity of the sensor was checked against various interferences, including ascorbic acid, uric acid, acetaminophen and other sugars, in all cases with excellent results. The feasibility of using this sensor for practical applications was successfully confirmed by determining the glucose concentration in different commercial beverages.     

基于纳米金的分子印迹传感器检测果蔬中的氧化乐果和乐果

以甲基丙烯酸为功能单体,氧化乐果为印迹分子,构建了一种可用于检测果蔬中氧化乐果和乐果的分子印迹传感器.在金电极上电沉积金纳米粒子,然后将修饰电极浸入10 mL含有氧化乐果和甲基丙烯酸的聚合物溶液中进行9次循环电聚合(-0.3～0.3 V),无水甲醇/乙酸洗涤除去模板分子.循环伏安法和电化学阻抗谱表征传感器,差分脉冲伏安...     

Towards the development of a portable sensor based on a molecularly imprinted membrane for the rapid determination of salbutamol in pig urine

A new type of conductometric probe based on a molecularly imprinted membrane (MIM) for the detection of salbutamol has been designed and fabricated. The probe consists of two parallel screen-printed electrodes (SPE). One of the SPEs was coated with a molecularly imprinted membrane using salbutamol as the template, and the other was modified with a non-molecularly imprinted membrane (N-MIM). Measurements of salbutamol were conducted after the conductometric probe had been connected to a commercial portable conductometer. Multi-sample or successive detections could be easily accomplished by replacing the one-off SPE coated with the salbutamol molecularly imprinted membrane with a new one. The conductometric response of the sensor to the concentration of salbutamol displayed a linear correlation over a range from 50 to 280 nM, with a detection limit of 13.5 nM. The recoveries reached 92.1-98.3% based on pig urine samples. In addition, the sensor based on this new type of probe demonstrated high sensitivity and selectivity for salbutamol.     

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。     

基于碳纳米管-石墨烯纳米片复合膜修饰金电极同时测定邻苯二酚和对苯二酚

制备了一种碳纳米管-石墨烯纳米片复合膜修饰金电极的用于同时测定邻苯二酚和对苯二酚电化学传感器。 并应用循环伏安法研究了邻苯二酚和对苯二酚在该电极上的电化学行为,邻苯二酚和对苯二酚的浓度检测采用差分脉冲伏安法,结果表明,碳纳米管-石墨烯纳米片复合膜极大的增强了邻苯二酚和对苯二酚的电催化活性。 并在0.5~6.0×10-4 mol/L浓度范围内与响应电流有良好的线性关系。邻苯二酚和对苯二酚的最低检测限分别是5.0×10-9和4.8×10-9 mol/L。 该电化学传感器能用于实际样品中的酚类化合物的检测。     

基于石墨烯分子印迹电化学传感器测定芦丁

将石墨烯(GR)滴涂至裸Au电极表面,并以邻氨基酚为功能单体,芦丁为模板分子,制备了芦丁分子印迹膜电化学传感器,利用循环伏安法(CV)和差分脉冲伏安法(DPV)对制得的传感器进行了电化学性能研究,并且对制备条件和测定条件进行了优化。结果表明,与裸Au电极相比,该GR修饰的Au电极在[Fe(CN)_6]~(3-/4-)溶液中峰电流明显增大,显著提高了芦丁分子印迹传感器的灵敏度。在最优实验条件下,基于GR分子印迹电化学传感器在4.40×10~(-6)~2.80×10~(-4) mol/L范围内呈良好的线性关系,检测限为1.46×10~(-6) mol/L。用该传感器测定了黑茶中芦丁的含量,获得较好结果。     

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.