细胞色素c／L-半胱氨酸修饰金电极检测亚硝酸根

采用循环伏安法、交流阻抗法研究了组装在L-半胱氨酸(L-Cys)修饰金电极上的细胞色素c(Cyt c)电化学行为;采用电化学方法以及紫外-可见光谱对电极进行表征.结果表明:通过静电吸附作用组装在L-Cys修饰金电极上的细胞色素c保持了良好的生物和电化学活性,用Cyt c/L-Cys修饰金电极检测亚硝酸根,响应电流与亚硝酸根浓度在5.0×10-6～4.5×10-4mol·L-1范围内呈线性关系,线性回归方程为Ip=0.031 c 8.165×10-6,相关系数为0.999 5,检出限(S/N=3)为1.5×10-7mol·L-1.电极用于模拟样品及咸菜样品中亚硝酸根的测定,回收率为89.0%～116.0%.     

亚硒酸钠在L-半胱氨酸自组装类生物膜修饰电极上的电化学行为

利用L-半胱氨酸自组装膜修饰金电极(L-Cys,Au/SAMs), 在0.05mol/L H_2SO_4 底液中研究了 Na_2SeO_3 的电化学特性.在0.00～1.30 V (vs. SCE) 电位范围内对微量Na_2SeO_3进行循环伏安扫描,发现L-Cys, Au/SAMs修饰电极在峰电位0.89 V处有灵敏的Se的氧化溶出峰.通过比较裸金电极和修饰电极在Na_2SeO_3 溶液中的电化学特性发现,修饰电极通过巯基中的S与Na_2SeO_3发生氧化还原作用生成Se,且修饰电极对沉积在电极表面的Se的氧化过程具有催化作用.根据Na_2SeO_3在单分子膜上的电化学行为,提出了单分子膜中硫(Au-S)与Se(Ⅳ)作用生成Se的反应机理、Se电化学催化氧化机理及巯基化合物通过生成纳米硒生物吸收Se的类生物膜模型.     

掺杂多壁碳纳米管改性聚溴甲酚绿膜修饰电极的制备、表征与应用研究

研究了掺杂多壁碳纳米管(MWNT)改性聚溴甲酚绿膜(PBG),以不同修饰方法制备了4种修饰电极,用扫描电镜、交流阻抗及循环伏安法等对电极进行表征。结果表明:4种修饰电极的电活化面积均得到明显提高,其中以层层修饰制备的聚溴甲酚绿膜/多壁碳纳米管复合膜(PBG/MWNT/GC)电极最能发挥MWNT和PBG的电活性。将电极用于8-羟基喹啉(8-HQ)电化学行为的研究,结果表明:4种修饰电极的伏安响应明显提高,且8-HQ在PBG/MWNT/GC上的氧化峰电位负移最多,峰电流最大,约为裸玻碳电极的4.5倍,电催化作用显著增强。8-HQ在PBG/MWNT/GC上电极反应的电子转移数和质子数均为1,是吸附控制的不可逆电氧化过程,氧化峰电流Ip与浓度c在4.0×10-6～3.5×10-4mol/L范围内呈良好的线性关系,r=-0.997 2,检出限(S/N=3)为1.96×10-8mol/L。PBG/MWNT/GC修饰电极可实现8-HQ的快捷、简便测定。     

一种基于碳纳米管的色氨酸传感器

研究了色氨酸(tryptophan即Trp)在多壁碳纳米管修饰玻碳电极(MWNTs/GC)上的电化学行为。MWNTs/GC电极对Trp具有良好的电催化作用,相对于GC电极,Trp在MWNTs/GC上峰电位负移128 mV,峰电流约为GC电极上氧化峰电流的31倍。在1.0 mol/L H2SO4中清洗能更新电极表面,消除产物吸附带来的影响。MWNTs/GC电极在含1.0×10-4mol/L Trp的缓冲溶液中闭路富集2 min时电流达到稳定值。研究了不同pH值影响的结果表明,参与电极反应的质子数和电子数相等。在pH=2.2时,Trp的氧化电流最大。利用LSV研究了电流与扫描速率的关系,结果表明,Trp在修饰电极上的氧化过程为扩散控制过程。在环境温度低于45℃时,随着温度增加,氧化电流逐渐增大。温度在16~35℃范围内,传感器的响应电流与温度成线性关系,温度系数为0.695μA/℃,说明此传感器在实测过程中因温度波动带来的测量误差很小。利用LSV研究了氧化峰电流与Trp的浓度关系的结果显示,峰电流与Trp的浓度在1.00×10-6~1.00×10-4mol/L范围内呈良好线性关系,检出限为1.82×10-7mol/L(S/N=3)。该电极具有良好的灵敏度、选择性和稳定性,放置7 d后,碳纳米管的峰电流仍能达到最初电流的98%。     

吲哚乙酸在纳米金/碳纳米管/壳聚糖修饰玻碳电极上的电化学行为及其检测

以壳聚糖(CS)为多壁碳纳米管(MWNTs)的分散介质, 通过MWNTs/CS膜上大量氨基静电吸附纳米金粒子(nanoAu), 使玻碳电极(GCE)表面形成稳定的nanoAu-MWNTs-CS-GCE修饰层, 并采用电化学方法初步研究了该修饰电极的性能. 探讨了吲哚乙酸(IAA)在该修饰电极上的电化学行为, 结果表明, 在5～200 μmol/L浓度范围内以及0.78 V电位条件下, 以循环伏安法(CV)测得的氧化峰电流变化值与c(IAA)呈良好的线性关系, 其回归方程为y=2.34×10^-4+0.14x, 检出限为8.33×10^-6 mol/L, 相关系数为0.9997.     

基于聚锂均苯三甲酸/多壁碳纳米管复合膜的葡萄糖生物传感器的研究

利用电聚合方法在裸玻碳(GC)电极上修饰一种新型金属有机框架化合物锂均苯三甲酸(Li-BTC),并采用滴涂技术制备了Nafion/GOx/MWNTs/poly-Li-BTC/GC葡萄糖生物传感器。利用扫描电镜分析了复合膜(含MWNTs和poly-Li-BTC)的形貌,采用循环伏安和交流阻抗方法对修饰电极的电化学性能进行了研究。结果表明,此复合膜可增大裸玻碳电极的有效表面积、改善电极的电催化活性。利用循环伏安法和计时安培法研究了葡萄糖在Nafion/GOx/MWNTs/poly-Li-BTC/GC电极上的电化学特性。结果表明:葡萄糖的浓度在0.02～1.56 mmol/L范围内,此修饰电极的电流响应与葡萄糖的浓度呈线性关系,其相关系数为0.9992,检出限为5.1μmol/L(信噪比为3∶1)。修饰电极的米氏常数为0.832 mmol/L,回收率为96.3#～100.3#。本研究制备的葡萄糖生物传感器具有较好的重复性、重现性、选择性与稳定性,用于葡萄糖注射液中葡萄糖含量的检测,结果满意。     

N-CTS/MWNTs/GCE电化学传感器对多巴胺和槲皮素的检测

通过N-酰化壳聚糖(N-CTS)与多壁碳纳米管(MWNTs)复合修饰玻碳电极得到N-CTS/MWNTs/GCE电化学传感器。采用循环伏安法研究了多巴胺(DA)和槲皮素(QU)在修饰电极上电化学行为。结果表明:NCTS/MWNTs/GCE电极能显著提高DA、QU的氧化峰电流,降低其氧化峰电位。在p H分别为7.38、6.80磷酸盐缓冲溶液中,DA、QU的氧化峰电流与浓度存在线性关系,线性方程分别为:Ip(DA)=0.0397+4715.8673 c、Ip(QU)=-0.2645+256.8935 c,相关系数均大于0.997,多巴胺、槲皮素检测限分别达1.0×10-8mol·L~(-1)和1.0×10-6mol·L~(-1)。N-CTS/MWNTs/GCE电极具有较好的重现性、稳定性,相对标准偏差为1.51%。该修饰电极可用于含DA、QU成分药物的直接测定。     

基于有序介孔碳/纳米金/L-半胱氨酸修饰电极测定铜(Ⅱ)

将纳米金(NG)电沉积在有序介孔碳(OMC)修饰玻碳电极表面,并将L-半胱氨酸(L-Cys)自组装至OM C/NG修饰电极表面,制备了OM C/NG/L-Cys修饰电极。采用透射电子显微镜考察了OM C的结构,扫描电子显微镜研究了OMC/NG/L-Cys修饰电极的表面形貌。考察了Cu2+在该修饰电极上的电化学行为,优化了Cu2+的测定条件。在最优条件下,溶出峰峰电流与Cu2+浓度在0.05~6.0μmol/L范围内呈良好线性关系,检出限为0.03μmol/L(S/N=3)。方法用于河水样品分析,其加标回收率在92.7%~101.6%之间。     

血红蛋白在纳米孔径氧化铝膜修饰电极上的直接电化学

运用电化学包埋法成功将血红蛋白(Hb)固定于纳米孔阳极氧化铝膜(AAO)修饰的玻碳电极(GC)表面, 制得Hb/PPy/AAO/GC修饰电极, 并对Hb/PPy/AAO/GC修饰电极的制备条件进行了优化. 研究了Hb/PPy/AAO/GC修饰电极在磷酸缓冲液(pH＝6.8)中的电化学行为, 探讨了血红蛋白在AAO修饰电极表面的直接电子转移机理. 结果表明阳极氧化铝膜不仅保持了血红蛋白的生物活性, 而且通过它的纳米尺寸效应, 实现了Hb与电极之间的直接电子转移. 其研究内容对生命科学和临床医学有着重要意义.     

石墨烯-壳聚糖/金纳米粒子修饰电极同时测定亚硫酸根和亚硝酸根

采用滴涂法得到了石墨烯(GR)-壳聚糖(CS)修饰的玻碳电极(GCE),再采用电沉积的方法将HAuCl4直接还原成金纳米粒子,沉积在GR-CS表面,制得了GR-CS/AuNPs GCE修饰电极。采用透射电子显微镜(TEM)分别对制备的GR和构建的修饰电极GR-CS/AuNPs GCE进行了形貌表征。用循环伏安法研究了SO32-和NO2-在GR-CS/AuNPs GCE上的电化学行为。结果表明,此修饰电极对SO32-和NO2-均有较好的电催化活性作用,并且能实现对两种物质的同时测定,SO32-和NO2-在该修饰电极上的线性范围分别为5～410μmol/L和1～380μmol/L,检出限(S/N=3)分别为1.0和0.25μmol/L。GR-CS/AuNPs GCE具有很好的稳定性、重现性和灵敏度。此电极用于实际水样的SO32-和NO2-的含量测定,回收率为97.2%～102.6%,结果令人满意。     

pMB/MWNTs/GC电极对水体中苯二酚异构体的同时测定

通过在多壁碳纳米管修饰玻碳电极上电聚合亚甲基蓝,制备了聚亚甲基蓝/碳纳米管/玻碳电极(pMB/MWNTs/GC)。用循环伏安法研究了3种苯二酚异构体在该电极上的电化学行为,结果表明,在pH7.0的磷酸盐缓冲溶液中,该修饰电极对苯二酚异构体的氧化表现出优异的电催化性能和选择性,对苯二酚、邻苯二酚和间苯二酚的氧化峰分别为0.104、0.203、0.609 V(vs.SCE),峰电位差值分别为99、406 mV。基于苯二酚异构体在pMB/MWNTs/GC修饰电极上的伏安行为,建立了苯二酚3种异构体同时分析的新方法。考察了各影响因素对测定的影响,最优实验条件下,在5.0×10-6~1.5×10-4mol.L-1范围内,3种苯二酚异构体的阳极峰电流与其浓度存在线性关系,检出限均为1.0×10-6mol.L-1。将该法用于水体及冲洗废液中苯二酚异构体含量的测定,结果满意。     

对氯酚在碳纳米管修饰玻碳电极上的电化学行为研究

研究了对氯酚在多壁碳纳米管修饰玻碳电极（MWNTs/GC）上的电化学行为。MWNTs/GC电极对对氯酚具有良好的电催化作用,相比玻碳电极对氯酚的氧化峰电位负移76 mV,峰电流达到玻碳电极上的8倍。通过线性扫描伏安法研究了富集时间、溶液pH和扫描速率对对氯酚氧化的影响。并采用计时电流法研究了氧化峰电流与对氯酚的浓度关系,结果显示峰电流与对氯酚的浓度在2.0×10^-7-2.0×10^-4mol/L范围内呈良好线性关系,检出限为8.8×10-8mol/L（S/N=3）。放置7 d后,对氯酚在碳纳米管上的峰电流仍能达到最初电流的96.2%,表明电极的稳定性较好。     

Amperometric Biosensors for Glucose Based on Layer‐by‐Layer Assembled Functionalized Carbon Nanotube and Poly (Neutral Red) Multilayer Film

Abstract

Multiwalled carbon nanotubes (MWNTs) were treated with a mixture of concentrated sulfuric and nitric acid to introduce carboxylic acid groups to the nanotubes. Conducting polymer film was prepared by electrochemical polymerization of neutral red (NR). By using a layer‐by‐layer method, homogeneous and stable MWNTs and poly (neutral red) (PNR) multilayer films were alternately assembled on glassy carbon (GC) electrodes. With the introduction of PNR, the MWNTs/PNR multilayer film system showed synergy between the MWNTs and PNR, with a significant improvement of redox activity due to the excellent electron‐transfer ability of carbon nanotubes (CNTs) and PNR. The electropolymerization is advantageous, providing both prolonged long‐term stability and improved catalytic activity of the resulting modified electrodes. The MWNTs/PNR multilayer film modified glassy carbon electrode allows low potential detection of hydrogen peroxide with high sensitivity and fast response time. As compared to MWNTs and PNR‐modified GC electrodes, the magnitude of the amperometric response of the MWNTs/PNR composite‐modified GC electrode is more than three‐fold greater than that of the MWNTs modified GC electrode, and nine‐fold greater than that of the PNR‐modified GC electrode. With the immobilization of glucose oxidase onto the electrode surface using glutaric dialdehyde, a biosensor that responds sensitively to glucose has been constructed. In pH 6.98 phosphate buffer, nearly interference‐free determination of glucose has been realized at ?0.2 V vs. SCE with a linear range from 50 µM to 10 mM and response time <10s. The detection limit was 10 µM glucose (S/N=3).     

金纳米粒子比色测定细胞色素c构象变化

金纳米粒子(AuNPs)的颜色会随着细胞色素c(Cytc)构象变化而发生较大的变化,作者在改变原测定流程的基础上利用这种有规律的变化研究和测定了H+和L-半胱氨酸(L-Cys)对Cytc的构象变化.实验中分别加入pH=1-13的Cytc,可以使AuNPs显示青、蓝、紫、红等明显不同的颜色,从而可以利用AuNPs比色快速测定不同pH值的Cytc构象变化.在pH=7时,当附加L-Cys浓度从低浓度变化到高浓度时,AuNPs颜色逐渐从紫色变化到蓝色、青色,从而实现利用AuNPs比色测定由L-Cys所引起Cytc构象变化.圆二色(CD)光谱证实了pH=1-13和不同浓度L-Cys下的Cytc构象变化.借助紫外-可见吸收光谱和扫描电子显微镜(SEM)进一步明确了加入Cytc后AuNPs的不同聚集状态与其颜色变化的关系.     

New Nanocomposite Based on Prussian Blue Nanoparticles/Carbon Nanotubes/Chitosan and Its Application for Assembling of Amperometric Glucose Biosensor

Abstract

A new nanocomposite was developed by combination of prussian blue (PB) nanoparticles and multiwalled carbon nanotubes (MWNTs) in the matrix of biopolymer chitosan (CHIT). The PB and MWNTs had a synergistic electrocatalytic effect toward the reduction of hydrogen peroxide. The CHIT/MWNTs/PB nanocomposite‐modified glassy carbon (GC) electrode could amplify the reduction current of hydrogen peroxide by ～35 times compared with that of CHIT/MWNTs/GC electrode and reduce the response time from ～60 s for CHIT/PB/GC to 3 s. Besides, the CHIT/MWNTs/PB nanocomposite‐modified GC electrode could reduce hydrogen peroxide at a much lower applied potential and inhibit the responses of interferents such as ascorbic acid (AA) uric acid (UA) and acetaminophen (AC). With glucose oxidase (GOx) as an enzyme model, a new glucose biosensor was fabricated. The biosensor exhibited excellent sensitivity (the detection limit is down to 2.5 µM), fast response time (less than 5 s), wide linear range (from 4 µM to 2 mM), and good selection.     

Electrochemical sensor for naphthols based on gold nanoparticles/hollow nitrogen-doped carbon microsphere hybrids functionalized with SH-β-cyclodextrin

Due to awfully harmful to the environment and human health, the qualitative and quantitative determinations of naphthols [1-naphthol (1-NAP) and 2-naphthol (2-NAP)] are of great significance and receive great attention. In this paper, gold nanoparticles (AuNPs)/hollow nitrogen-doped carbon microspheres (HNCMS) hybrids (AuNPs/HNCMS) were prepared and functionalized with thiolated-β-cyclodextrin (HS-β-CD) for the first time, and then applied successfully in sensitive and simultaneous electrochemical detection of naphthols. The results show that the oxidation peak currents of naphthols obtained on the HS-β-CD/AuNPs/HNCMS modified glassy carbon (GC) electrode are much higher than that on the AuNPs/HNCMS/GC, HNCMS/GC and bare GC electrodes. Additionally, compared with other electrochemical sensors developed previously, the proposed electrode results in improved detection limits of about four times for 1-NAP (1.0 nM) and two orders of magnitude for 2-NAP (1.2 nM). The linear response ranges of both 1-NAP and 2-NAP are 2–150 nM.     

Direct electrochemistry and electrocatalysis of cytochrome c immobilized on gold nanoparticles-chitosan-carbon nanotubes-modified electrode

A robust and effective nanohybrid film based on gold nanoparticles (GNPs)/chitosan (Chit)/multi-walled carbon nanotubes (MWNTs) was prepared by a layer-by-layer self-assembly technique. Cytochrome c (Cyt c) was successfully immobilized on the nanohybrid film modified glassy carbon (GC) electrode by cyclic voltammetry. The direct electron transfer between Cyt c and the modified electrode was investigated in detail. Cyt c shows a couple of quasi-reversible and well-defined cyclic voltammetry peaks with a formal potential (E^0′) of −0.16 V (versus Ag/AgCl) in pH 7.0 phosphate buffer solution (PBS). The Cyt c/GNPs/Chit/MWNTs modified GC electrode gives an improved electrocatalytic activity towards the reduction of hydrogen peroxide (H₂O₂). The sensitivity is 92.21 μA mM⁻¹ cm⁻² and the calculated apparent Michaelis-Menten constant () is 0.791 mM, indicating a high-catalytic activity of Cyt c. The catalysis currents increase linearly to the H₂O₂ concentration in a wide range of 1.5 × 10⁻⁶ to 5.1 × 10⁻⁴ M with a correlation coefficient 0.999. The detection limit is 9.0 × 10⁻⁷ M (at the ratio of signal to noise, S/N = 3). Moreover, the modified electrode displays rapid response (5 s) to H₂O₂, and possesses good stability and reproducibility.     

Chemometrics to evaluate the quality of water sources for human consumption

Multilayer films of multiwalled carbon nanotubes (MWNTs) were homogeneously and stably assembled on a glassy carbon (GC) electrode using the layer-by-layer (LBL) method based on electrostatic interaction between MWNTs (negatively charged) and a biopolymer chitosan (CHIT) (positively charged). Scanning electron microscopy (SEM) image of the resulting {CHIT/MWNTs}₉ film indicated that the substrate was mostly covered with MWNTs in the form of small bundles or single nanotubes. The multilayer film was used to study the electrocatalytic oxidation of NADH. The assembled {CHIT/MWNTs}₉/GC electrode could decrease the oxidation overpotential of NADH by more than 350 mV. The {CHIT/MWNTs}₉/GC electrode exhibited a wide linear response range of 8 × 10⁻⁷ to 1.6 × 10⁻³ mol · L⁻¹ with a correlation coefficient of 0.997 for the detection of NADH. The response time and detection limit (S/N = 3) were determined to be 3 s and 0.3 × 10⁻⁶ mol · L⁻¹, respectively. Another attractive characteristic was that the method was simple and the assembled {CHIT/MWNTs}₉/GC electrode was highly stable.     

Direct electron transfer of cytochrome c and its biosensor based on gold nanoparticles/room temperature ionic liquid/carbon nanotubes composite film

A robust and effective composite film based on gold nanoparticles (GNPs)/room temperature ionic liquid (RTIL)/multi-wall carbon nanotubes (MWNTs) modified glassy carbon (GC) electrode was prepared by a layer-by-layer self-assembly technique. Cytochrome c (Cyt c) was successfully immobilized on the RTIL-nanohybrid film modified GC electrode by electrostatic adsorption. Direct electrochemistry and electrocatalysis of Cyt c were investigated. The results suggested that Cyt c could be tightly adsorbed on the modified electrode. A pair of well-defined quasi-reversible redox peaks of Cyt c was obtained in 0.10 M, pH 7.0 phosphate buffer solution (PBS). RTIL-nanohybrid film showed an obvious promotion for the direct electron transfer between Cyt c and the underlying electrode. The immobilized Cyt c exhibited an excellent electrocatalytic activity towards the reduction of H₂O₂. The catalysis currents increased linearly to the H₂O₂ concentration in a wide range of 5.0 × 10⁻⁵– 1.15 × 10⁻³ M. Based on the multilayer film, the third-generation biosensor could be constructed for the determination of H₂O₂.     

Determination of silver in geological samples using high-resolution continuum source electrothermal atomic absorption spectrometry and direct solid sampling

A DNA biosensor was constructed by immobilizing DNA on a glassy carbon (GC) electrode modified with multiwall carbon nanotubes (MWNTs) dispersed in Nafion (DNA/MWNTs/GCE). The DNA-modified electrode exhibited two well-defined oxidation peaks corresponding to the guanine and adenine residues of DNA, respectively. The effects of the adsorption potential, DNA concentration and quantity of MWNTs used for DNA immobilization were investigated, as were the effects of buffer, pH and scan rate on the voltammetric behavior of DNA. Phenol, m-cresol and catechol showed noticeable inhibition towards the response of the electrode due to their interactions with DNA. These findings were used to design biosensors with linear response to these phenolic pollutants.