Nafion修饰玻碳电极伏安法测定痕量锡

报道了一种用Nafion修饰玻碳电极测定痕量锡的新方法。研究了Nafion膜的有关特性和测定的优化条件,当富集时间为3min时,峰电流与Sn(Ⅳ)浓度在1×10-9~1×10-7mol/L的范围呈良好的线性关系,检测限为2.46×10-10mol/L。该法用于实际水样中痕量锡的测定,平均回收率为97.24%。     

溶剂挥发诱导苯丙氨酸二肽自组装结构的电化学生物传感研究

将乙腈诱导苯丙氨酸二肽自组装生成的蒲公英状微晶聚集体修饰于玻碳电极上作为酶载体,采用戊二醛交联固定辣根过氧化物酶(HRP),Nafion溶液包埋保护HRP,制备过氧化氢生物传感器。该传感器对H2O2表现出良好的催化还原特性,其响应线性范围为5.0×10-7～6.0×10-4mol/L,检出限为2.5×10-7mol/L(S/N=3)。米氏常数为0.83 mmol/L,表明所固定的酶具有较高的生物活性,且与过氧化氢有较强的亲和能力。这种采用寡肽自组装产物修饰电极的方法也可为制备其他酶传感器提供借鉴。     

杯芳烃修饰主客体化学传感器研究——对甲酚的测定

以C—十一烷基间苯二酚杯 (6 )芳烃作为主体分子 ,修饰玻碳电极上制成的一种主客体化学传感器 ,并用其对溶液中的客体分子———对甲酚进行测定。该电极具有良好的选择性 ,对 5 .0× 10 -5～2 .0× 10 -3 mol/L的对甲酚具有很好的线性响应 ,检测下限为 3.0× 10 -5mol/L ,同时对修饰前后玻碳电极的表面状态进行了研究     

脉冲电沉积氧化石墨烯纳米带修饰电极测定盐酸四环素

以多壁碳纳米管为原料制备氧化石墨烯纳米带(GONRs),通过红外光谱、紫外-可见吸收光谱和拉曼光谱对其进行表征。将制备好的GONRs脉冲电沉积到玻碳电极(GCE)表面制备修饰电极(GONRs/GCE),研究了盐酸四环素(TC)在GONRs/GCE上的电化学行为。结果表明,与裸玻碳电极相比,GONRs/GCE对TC有更高的电催化活性。TC在GONRs/GCE上发生受吸附控制的不可逆氧化反应,且在pH 3.0的柠檬酸-柠檬酸钠缓冲溶液中氧化峰电流最高。优化条件下,TC的氧化峰电流与浓度线性相关,线性范围为4.0×10~(-7)～1.0×10~(-4) mol/L,最低检测限为2.0×10~(-7) mol/L(S/N=3)。将该电极用于河水样品中TC的检测,加标回收率为97.2%～104.1%。     

自组装纳/微分级结构CoNi前驱体多孔微球对氢醌的选择性检测

开发了一种基于玻碳电极(GCE)表面修饰钴镍前驱体多孔微球(CoNiP/GCE)的电化学传感器,用于选择性测定氢醌。通过SEM、XRD和BET等多种手段对CoNi前驱体进行了表征。运用循环伏安法和示差脉冲伏安法研究氢醌在CoNiP/GCE表面的电化学性能。结果表明:CoNiP/GCE对氢醌有良好的电催化氧化性能。在0.5～5.0 mmol/L检测范围内,DPV峰电流与不同浓度氢醌展现了较好的线性关系,R~2=0.996 8,检测限为3.5μmol/L。此外,修饰电极能够在强干扰物质多巴胺的存在下实现对氢醌的特异性检测,检测范围是0.2～1.8 mmol/L,检测限为2.29μmol/L,R~2=0.992 8。CoNiP/GCE具有良好的选择性和抗干扰能力,适合进一步开发用于生物样品中氢醌检测的传感器。     

一步法电沉积制备纳米金/碳纳米管修饰电极及对邻苯二酚电催化性能研究

以羧基化碳纳米管(CNT-COOH)溶液作为支持电解质,采用多电位阶跃电沉积方法将CNTs和纳米金同步直接沉积到玻碳电极表面,制备了对邻苯二酚(CAT)具有很高的电催化氧化作用的纳米金-碳纳米管修饰电极(Au/CNTs/GCE),其催化效果强于单独的金纳米粒子或碳纳米管修饰电极。通过优化沉积时间、pH和扫速对修饰电极的影响,并考察了在最佳条件下CAT在Au/CNTs/GCE修饰电极上的电化学行为,发现CAT在该修饰电极上发生可逆的氧化还原反应,响应电流与浓度在4.0×10-6～8.0×10-5mol/L和1.0×10-4～1.0×10-3mol/L范围内呈线性关系,相关系数分别为0.9996和0.9985,检出限为4.5×10-7mol/L(S/N)。     

基于适配体复合膜电化学传感器测定莱克多巴胺的研究

应用多壁碳纳米管(MWCNTs)、L-精氨酸(L-Arg)和纳米金(Au NPs)修饰玻碳电极(GCE)获得Au NPs/P-L-Arg/MWCNTs/GCE修饰电极,通过静电作用将氨基修饰的莱克多巴胺(RAC)适配体固定于电极表面,制得新型莱克多巴胺适配体电化学传感器。考查了扫描速度、培育温度、培育时间、适配体修饰量以及p H等条件对传感器响应性能的影响。结果表明,该传感器灵敏度高、选择性好。在优化条件下,其线性范围为1.00×10-11~1.00×10-7mol/L,线性相关系数为0.980 4,检出限达1.00×10-11mol/L。另外,该传感器操作简单、性能稳定,将其用于实际猪尿中莱克多巴胺的检测,回收率为97.1%~103.0%,相对标准偏差低于9.4%。     

多菌灵在多壁碳纳米管-聚4-(2-吡啶偶氮)间苯二酚膜修饰电极上的电化学行为及测定

制备了多壁碳纳米管-聚4-(2-吡啶偶氮)间苯二酚膜修饰电极,利用扫描电镜对新的复合膜修饰电极(PAR-MWNT/GCE)进行表征,研究了在多菌灵的循环伏安曲线以及它的差分脉冲伏安曲线。结果表明,该修饰电极对多菌灵具有良好的电催化作用。在8.0×10-6~2.06×10-4 mol/L浓度范围内,多菌灵的差分脉冲伏安法的峰电流和浓度呈现良好的线性关系,相关系数为0.997 11,检出限为2.5×10-7 mol/L(S/N=3)。PAR-MWNT/GCE复合物修饰电极可快速、简洁、方便的测定多菌灵的浓度。     

钯/石墨烯/离子液体纳米复合物的过氧化氢电化学传感器

将一定比例的石墨烯(GN)与离子液体(IL)1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF6)超声混匀GN-IL,并滴涂在玻碳电极(GC)上,然后通过电沉积法在此电极上沉积钯纳米颗粒制得Pb/GN-IL/GC修饰电极。采用循环伏安法和计时电流法研究了该传感器对H2O2的电催化还原行为。结果表明,与IR修饰电极和石墨烯修饰电极相比,该电极对H2O2具有更好的电催化活性。此传感器对过氧化氢检测的线性范围为4.0×10-6~4.3×10-4mol/L,检出限为2.1×10-6mol/L。     

水热法制备二氧化锰及在过氧化氢传感器中的应用

以高锰酸钾、硫酸锰、过硫酸钠等为原料,采用水热法合成了一系列二氧化锰(MnO_2)催化剂,通过X射线衍射分析(XRD)、扫描电镜(SEM)以及N_2吸附-脱附等手段进行了表征。后将一定量的二氧化锰材料与Nafion混合后滴涂于玻碳电极(GCE)表面,构成了一系列新型的过氧化氢传感器。并采用循环伏安法(CV)和计时电流法(I-t)分别对修饰电极进行表征,考察其相应的传感性能。结果表明,海胆状α-MnO_2催化剂修饰的玻碳电极对过氧化氢有优异的电催化性能,其灵敏度为26.2μA·L/mmol。H2O2峰电流值在(2×10~(–6))~(0.14×10~(–3))mol/L范围内与浓度呈线性关系,最低检出限为0.57×10~(–6)mol/L(S/N=3)。     

Preparation of yttrium hexacyanoferrate/carbon nanotube/Nafion nanocomposite film-modified electrode: Application to the electrocatalytic oxidation of l-cysteine

An yttrium hexacyanoferrate nanoparticle/multi-walled carbon nanotube/Nafion (YHCFNP/MWNT/Nafion)-modified glassy carbon electrode (GCE) was constructed. Several techniques, including infrared spectroscopy, energy dispersive spectrometry, scanning electron microscopy and electrochemistry, were performed to characterize the yttrium hexacyanoferrate nanoparticles. The electrochemical behavior of the YHCFNP/MWNT/Nafion-modified GCE in response to l-cysteine oxidation was studied. The response current of l-cysteine oxidation at the YHCFNP/MWNT/Nafion-modified GCE was obviously higher than that at the bare GCE or other modified GCE. The effects of pH, scan rate and interference on the response to l-cysteine oxidation were investigated. In addition, on the basis of these findings, a determination of l-cysteine at the YHCFNP/MWNT/Nafion-modified GCE was carried out. Under the optimum experimental conditions, the electrochemical response to l-cysteine at the YHCFNP/MWNT/Nafion-modified GCE was fast (within 4 s). Linear calibration plots were obtained over the range of 0.20–11.4 μmol L⁻¹ with a low detection limit of 0.16 μmol L⁻¹. The YHCFNP/MWNT/Nafion-modified GCE exhibited several advantages, such as high stability and good resistance against interference by ascorbic acid and other oxidizable amino acids.     

Electrochemical reduction of dioxygen on a thioglycolic acid-capped CdTe quantum dots modified glassy carbon electrode

A novel modified electrode was constructed by immobilizing thioglycolic acid-capped CdTe quantum dots (QDs) on a glassy carbon electrode (GCE) using Nafion ionomers. The results obtained by electrochemical impedance spectroscopy, cyclic voltammetry, and rotating disk electrode using the modified QDs?CNafion/GCE in a 0.20?M phosphate buffer of pH 7.0 revealed that the QDs act as effective mediators for the electrocatalytic reduction of dioxygen.     

Characterization and electrochemical studies of Nafion/nano-TiO2 film modified electrodes

A nano-TiO₂ film from stable aqueous dispersion has been modified on a glassy carbon electrode (GCE), and was characterized by scanning electron microscopy (SEM) and surface-enhanced Raman spectroscopy (SERS). This nanostructured film exhibits an ability to improve the electron-transfer rate between electrode and dopamine (DA), and electrocatalyze the redox of DA. The electrocatalytical behavior of DA was examined by cyclic voltammetry (CV). Combined with Nafion, the bilayer-modified electrode (N/T/GCE) gives a sensitive voltammetric response of DA regardless of excess ascorbic acid (AA). Electrochemical impedance spectroscopy (EIS) at a fixed potential was performed at variously treated GCEs. The mechanism of the electrode reaction of DA at N/T/GCE and the equivalent circuits of different GCEs have been proposed.     

A sandwich electrochemical immunosensor using magnetic DNA nanoprobes for carcinoembryonic antigen

A novel magnetic nanoparticle-based electrochemical immunoassay of carcinoembryonic antigen (CEA) was designed as a model using CEA antibody-functionalized magnetic beads [DNA/Fe(3)O(4)/ZrO(2); Fe(3)O(4) (core)/ZrO(2) (shell) nano particles (ZMPs)] as immunosensing probes. To design the immunoassay, the CEA antibody and O-phenylenediamine (OPD) were initially immobilized on a chitosan/nano gold composite membrane on a glassy carbon electrode (GCE/CS-nano Au), which was used for CEA recognition. Then, horseradish peroxidase (HRP)-labeled anti-CEA antibodies (HRP-CEA Ab(2)) were bound to the surface of the synthesized magnetic ZMP nanoparticles as signal tag. Thus, the sandwich-type immune complex could be formed between secondary antibody (Ab(2)) modified DNA/ZMPs nanochains tagged by HRP and GCE/CS-nano Au. Unlike conventional nanoparticle-based electrochemical immunoassays, the recognition elements of this immunoassay included both electron mediators and enzyme labels, which obviously simplifies the electrochemical measurement process. The sandwich-type immunoassay format was used for online formation of the immunocomplex of CEA captured in the detection cell with an external magnet. The electrochemical signals derived from HRP during the reduction of H(2)O(2) with OPD as electron mediator were measured. The method displayed a high sensitivity for CEA detection in the range of 0.008-200 ng/mL, with a detection limit of 5 pg/mL (estimated at a signal-to-noise ratio of 3). The precision, reproducibility, and stability of the immunoassay were good. The use of the assay was evaluated with clinical serum samples, and the results were in excellent accordance with those obtained using the standard enzyme-linked immunosorbent assay (ELISA) method. Thus, the magnetic nanoparticle-based assay format is a promising approach for clinical applications, and it could be further developed for the detection of other biomarkers in cancer diagnosis.     

金纳米粒子修饰玻碳电极的电化学行为研究

利用层层自组装技术,通过有机偶联层胱胺将金纳米粒子修饰在玻碳电极上,得到金纳米粒子/胱胺/玻碳电极,并通过循环伏安法和电化学阻抗谱对修饰电极的电化学行为进行研究,结果表明该修饰电极具有优于裸玻碳电极的良好的电化学性能,可用于进一步的应用。     

Influence of the composition on the structure and electrochemical characteristics of the PEFC cathode

The influence the composition of the cathode has on its structure and electrochemical performance was investigated for a Nafion content spanning from 10 to 70 wt.%. The cathodes were formed on a Nafion membrane by the spray method and using 20 wt.% Pt on Vulcan (E-TEK). Materials characterisation (SEM, STEM, gas and mercury porosimetry, electron conductivity) and electrochemical characterisation (steady-state polarisation curve, impedance spectroscopy in O₂ and current-pulse measurements in N₂) were performed. The impedance spectra were analysed using our dynamic agglomerate model. The results indicate that the agglomerate model is valid until a Nafion content of about 45 wt.%. Pt/C and Nafion are homogeneously mixed for any composition and no Nafion film was observed. The cathodes containing 36–43 wt.% Nafion display a single or double Tafel slope behaviour ascribed to diffusion limitations in the agglomerates. At larger Nafion content, the agglomerate model can describe the curves only by assuming a diffusion coefficient 3–4 decades smaller than that of gases. At such compositions, the porosity was only 10%. These results were interpreted as a blocking of the pores and a non-percolating pore system for too large Nafion contents.     

Electrochemical synthesis of belt-like polyaniline network on p-phenylenediamine functionalized glassy carbon electrode and its use for the direct electrochemistry of horse heart cytochrome c

Three-dimension (3D) belt-like polyaniline (PAN) network has been prepared via electrochemical polymerization of aniline on p-phenylenediamine (PDA) functionalized glassy carbon electrode (GCE) using a three-step electrochemical deposition procedure. PDA was covalently binded on GCE via the formation of carbon-nitrogen bond between amine cation radical and the aromatic moiety of GCE surface using electrochemical oxidation procedure. X-ray photo-electron spectroscopy (XPS) and cyclic voltammetry have been performed to characterize the attachment of PDA on GCE. The images of scanning electron microscope (SEM) show that the 3D belt-like PAN network is uniform. The width and thickness of the PAN belt varies in the range of 1.5-5.5 μm and 0.1-0.8 μm, respectively. The distance between the belt-contacts ranges from 2.5 to 15 μm. The 3D belt-like PAN network modified GCE (PAN-PDA/GCE) exhibits an improved electro-activity of PAN at an extended pH up to 7.0. The PAN-PDA/GCE not only immobilizes but also leads to a direct electrochemical behavior of cytochrome c (Cyt c). The immobilized Cyt c maintains its activity, showing a surface-controlled electrode process with the electron-transfer rate constant (k_s) of 14.8 s⁻¹ and electron-transfer coefficient (α) of 0.48, and could be used for the electrocatalytic reduction of hydrogen peroxide (H₂O₂).     

A novel hydrogen peroxide biosensor based on Au-graphene-HRP-chitosan biocomposites

Graphene was prepared successfully by introducing -SO₃⁻ to separate the individual sheets. TEM, EDS and Raman spectroscopy were utilized to characterize the morphology and composition of graphene oxide and graphene. To construct the H₂O₂ biosensor, graphene and horseradish peroxidase (HRP) were co-immobilized into biocompatible polymer chitosan (CS), then a glassy carbon electrode (GCE) was modified by the biocomposite, followed by electrodeposition of Au nanoparticles on the surface to fabricate Au/graphene/HRP/CS/GCE. Cyclic voltammetry demonstrated that the direct electron transfer of HRP was realized, and the biosensor had an excellent performance in terms of electrocatalytic reduction towards H₂O₂. The biosensor showed high sensitivity and fast response upon the addition of H₂O₂, under the conditions of pH 6.5, potential −0.3 V. The time to reach the stable-state current was less than 3 s, and the linear range to H₂O₂ was from 5 × 10⁻⁶ M to 5.13 × 10⁻³ M with a detection limit of 1.7 × 10⁻⁶ M (S/N = 3). Moreover, the biosensor exhibited good reproducibility and long-term stability.     

Glassy carbon electrode modified with Nafion-Au colloids for clenbuterol electroanalysis

Stable Nafion-Au colloids were immobilized on a glassy carbon electrode (GCE) for detection of β-agonist clenbuterol by electroanalysis. The Au colloids were prepared by a one-step electrodeposition onto GCE, with obvious electrocatalytic activity present. The negatively charged Nafion film was an efficient barrier to negatively charged interfering compounds, resulting in accumulation of positively charged clenbuterol at the Nafion film. The electrochemical characters of the electrode during various modified steps in a redox probe system of K₄[Fe(CN)₆]/K₃[Fe(CN)₆] were confirmed by cyclic voltammetry (CV) and AC-impedance. In Britton-Robinson (B-R) buffer solution (pH = 2.0) and the potential range of −0.2 to 1.2 V, the Nafion-Au colloid modified electrode, compared to a bare GCE, exhibits obvious electrocatalytic activity towards the redox of clenbuterol by greatly enhancing the peak current with a linear calibration curve from 8.0 × 10⁻⁷ to 1.0 × 10⁻⁵ mol/L and a detection limit of (1.0 × 10⁻⁷ mol/L) (R = 0.996). The modified electrode shows high sensitivity, selectivity and reproducibility. The recovery for detecting clenbuterol (∼10⁻⁶ mol/L) in human serum is up to 98.19%.     

Electrodeposit nano-copper oxide on glassy carbon electrode for simultaneous detection of guanine and adenine

An electrochemical sensor was fabricated and used to simultaneously detect guanine and adenine. In this study, nano-copper oxide-modified glassy carbon electrode (nano-copper oxide/GCE) was prepared by electrodeposition. The nano-copper oxide/GCE was characterized by electrochemical impedance spectroscopy and scanning electron microscopy. The fabricated nano-copper oxide/GCE sensor exhibited sensitive response to guanine and adenine in 0.1 M PBS (pH 7.0). The anodic peak currents were linear with the guanine and adenine concentrations over the range of 0.05–1.2 μM with the correlation coefficients of 0.9997 and 0.9993, respectively, and the corresponding detection limits were 6 × 10⁻³ μM and 9 × 10⁻³ μM (S/N = 3), respectively. The nano-copper oxide/GCE could be applied to simultaneously detect guanine and adenine in samples with good anti-interference ability.