基于聚对苯二甲酸乙二醇酯薄膜的石墨烯/金纳米粒子/葡萄糖氧化酶柔性电极的制备及检测葡萄糖

采用化学气相沉积法生长多晶石墨烯(Graphene, G),转移至聚对苯二甲酸乙二醇酯(PET)薄膜表面,通过控制金溶胶蒸发速率,在多晶石墨烯表面组装均匀分布的亚单层金纳米粒子(AuNPs);然后修饰巯基乙酸,通过共价交联反应将葡萄糖氧化酶固定于AuNPs表面,构建基于PET膜的石墨烯/金纳米粒子/葡萄糖氧化酶(G/AuNPs/GOD)柔性电极.此电极在工作电位0.6 V(vs.SCE电极)、pH 7.0磷酸盐缓冲溶液、室温25℃条件下,差分脉冲伏安法响应电流与被测葡萄糖浓度在0.05~10.55 mmol/L范围内呈线性关系,线性方程为I(108A)=0.2629 C(mmol/L)+1.4149,线性相关系数 r=0.9955,检出限1 μmol/L (3σ). G/AuNPs/GOD柔性电极的制备可为特定环境和可穿戴设备的葡萄糖检测提供了新的途径和方法,拓展了葡萄糖检测的应用范围.     

以天青Ⅰ为介体的纳米金颗粒增强的葡萄糖传感器

采用层层自组装的方法和异种电荷互相吸引的原理,将Nafion修饰在金电极上固载带正电荷的天青Ⅰ,并利用天青Ⅰ中的氨基固载纳米金,再通过纳米金将酶固定在金电极表面,制成了葡萄糖传感器.采用循环伏安法和交流阻抗法,研究了金电极表面组装各层之后的电化学特征,以及电极对葡萄糖的电化学催化作用. 结果表明,天青Ⅰ不仅可以固定酶和纳米金,而且还可以在酶和电极之间有效地传递电子.在优化的实验条件下,该传感器对葡萄糖响应的线性范围为5.1×10-6 ~4.0×10-3 mol/L,检出限(S/N=3)为1.0 μmol/L.该生物传感器显示出较好的稳定性和抗干扰能力,将其用于人体血清中葡萄糖的测定,结果令人满意.     

Direct Electrochemistry of Glucose Oxidase Immobilized on Titanium Carbide‐Au Nanoparticles‐Fullerene C60 Composite Film and Its Biosensing for Glucose

The direct electrochemistry of glucose oxidase (GOD) immobilized on the designed titanium carbide‐Au nanoparticles‐fullerene C₆₀ composite film modified glassy carbon electrode (TiC‐AuNPs‐C₆₀/GCE) and its biosensing for glucose were investigated. UV‐visible and Fourier‐transform infrared spectra of the resulting GOD/TiC‐AuNPs‐C₆₀ composite film suggested that the immobilized GOD retained its original structure. The direct electron transfer behaviors of immobilized GOD at the GOD/TiC‐AuNPs‐C₆₀/GCE were investigated by cyclic voltammetry in which a pair of well‐defined, quasi‐reversible redox peaks with the formal potential (E^0′) of ‐0.484 V (vs. SCE) in phosphate buffer solution (0.05 M, pH 7.0) at the scan rate of 100 mV·s^?1 were obtained. The proposed GOD modified electrode exhibited an excellent electrocatalytic activity to the reduction of glucose, and the currents of glucose reduction peak were linearly related to glucose concentration in a wider linearity range from 5.0 × 10^?6 to 1.6 × 10^?4 M with a correlation coefficient of 0.9965 and a detection limit of 2.0 × 10^?6 M (S/N = 3). The sensitivity and the apparent Michaelis‐Menten constant (K_M^app) were determined to be 149.3 μA·mM^?1·cm^?2 and 6.2 × 10^?5 M, respectively. Thus, the protocol will have potential application in studying the electron transfer of enzyme and the design of novel electrochemical biosensors.     

The direct electrochemistry of glucose oxidase based on the synergic effect of amino acid ionic liquid and carbon nanotubes

Amino acid ionic liquids (AAILs) have attracted much attention due to their special chemical and physical properties, especially their outstanding biocompatibility and truly green aspect. In this work, a novel electrochemical biosensing platform based on AAILs/carbon nanotubes (CNTs) composite was fabricated. AAILs were used as a novel solvent for glucose oxidase (GOD) and the GOD-AAILs/CNTs/GC electrode was conveniently prepared by immersing the carbon nanotubes (CNTs) modified glassy carbon (GC) electrode into AAILs containing GOD. The direct electrochemistry of GOD on the GOD-AAILs/CNTs/GC electrode has been investigated and a pair of reversible peaks was obtained by cyclic voltammetry. The immobilized glucose oxidase could retain bioactivity and catalyze the reduction of dissolved oxygen. Due to the synergic effect of AAILs and CNTs, the GOD-AAILs/CNTs/GC electrode shows excellent electrocatalytic activity towards glucose with a linear range from 0.05 to 0.8 mM and a detection limit of 5.5 μM (S/N = 3). Furthermore, the biosensor exhibits good stability and ability to exclude the interference of commonly coexisting uric and ascorbic acid. Therefore, AAILs/CNTs composite can be a good candidate biocompatible material for the direct electrochemistry of the redox-active enzyme and the construction of third- generation enzyme sensors.     

基于表面重建螺旋型铂铱电极的葡萄糖生物传感器

通过对螺旋型铂铱电极表面进行化学腐蚀和电化学沉积铂纳米粒子实现电极表面的重建和优化,研究了螺旋型铂铱电极在不同腐蚀时间和电沉积时间下的形貌及对过氧化氢(H2O2)的催化活性.对表面重建的工作电极涂覆氧化酶和半透膜,制备出了铂纳米粒子/葡萄糖氧化酶/环氧聚氨酯酶电极,并将其用作葡萄糖传感器的工作电极.传感器计时电流检测结果表明,表面重建后的酶电极传感器对葡萄糖的检测范围扩大为2~45 mmol/L,优于裸铂铱酶电极传感器,电流响应值和灵敏度得到明显提升,同时传感器还具有良好的稳定性和选择性.     

Pulsed Deposited Manganese and Vanadium Oxide Film Modified with Carbon Nanotube and Gold Nanoparticle: Chitosan and Ionic Liquid‐based Biosensor

Present study describes the synthesis of mixed oxide films of manganese and vanadium by electrochemical pulsed deposition technique on a glassy carbon electrode (GCE) modified with multiwall carbon nanotubes (MWCNT). The film was further decorated with gold nanoparticles to enhance the reduction signal of dissolved oxygen in pH 5.17 acetate buffer solution. All of the electrochemical synthesized modified electrodes have been characterized with Scanning electron microscopy(SEM), High‐resolution transmission electron microscopy (HRTEM), X‐Ray photoelectron spectroscopy (XPS), X‐Ray diffraction (XRD) techniques. The electrode obtained (AuNPs/MnOx?VOx/CNT/GCE) was utilized as a platform for glucose biosensor where the glucose oxidase enzyme was immobilized on the composite film with the aid of chitosan and an ionic liquid. The electrochemical performance of the biosensor was investigated by cyclic voltammetry and the relative parameters have been optimized by amperometric measurements in pH 5.17 acetate buffer solution. The developed biosensor exhibited a linear range for glucose between 0.1–1.0 mM and the limit of detection was calculated as 0.02 mM.     

Direct electrochemistry of glucose oxidase immobilized on TiO2–graphene/nickel oxide nanocomposite film and its application

A novel electrochemical platform based on nickel oxide (NiO) nanoparticles and TiO₂–graphene (TiO₂–Gr) was developed for the direct electrochemistry of glucose oxidase (GOD). The electrochemical behavior of the sensor was studied using cyclic voltammetry and chronoamperometry. The experimental results demonstrated that the nanocomposite well retained the activity of GOD and the modified electrode GOD/NiO/TiO₂–Gr/GCE exhibited excellent electrocatalytic activity toward the redox of GOD as evidenced by the significant enhancement of redox peak currents in comparison with bare GCE. The biosensor responded linearly to glucose in the range of 1.0–12.0?mM, with a sensitivity of 4.129?μA?mM^?1 and a detection limit of 1.2?×?10^?6?M under optimized conditions. The response time of the biosensor was 3?s. In addition, the developed biosensor possessed good reproducibility and stability, and there was negligible interference from other electroactive components.     

Nafion coating the ferrocenylalkanethiol and encapsulated glucose oxidase electrode for amperometric glucose detection

This paper describes the fabrication and application of a complex electrode--Nafion film coating ferrocenylalkanethiol (FcC(11)SH) and encapsulated glucose oxidase (GOD) on a gold electrode. FcC(11)SH is employed as a mediator enabling the electron transfer between GOD and the electrode, GOD is encapsulated in polyacrylamide gel to improve the stability of the enzyme, and the Nafion film is coated on the modified electrode to eliminate interferents such as ascorbic acid, uric acid and acetaminophen in amperometric glucose detection. It is noticed that such a complex electrode exhibits excellent catalytic activity for glucose oxidation, and preserves the native structure of GOD and therefore its enzymatic activity. The encapsulated GOD retains more than 80% of its original biocatalytic activity even after 24 days, much longer than that of naked GOD molecules attached directly to the electrode. The oxidation peak current at the modified electrode shows a linear relationship with the glucose concentration in the range from 0.05 to 20 mM with a detection limit of 2.4 μM. In addition, the electrode displays a rapid response and good reproducibility for glucose detection, and has been successfully employed for glucose detection in blood plasma samples.     

A simple method to fabricate a chitosan-gold nanoparticles film and its application in glucose biosensor

A novel film of chitosan-gold nanoparticles is fabricated by a direct and facile electrochemical deposition method and its application in glucose biosensor is investigated. HAuCl(4) solution is mixed with chitosan and electrochemically reduced to gold nanoparticles, which can be stabilized by chitosan and electrodeposited onto glassy carbon electrode surfaces along with the electrodeposition of chitosan. Then a model enzyme, glucose oxidase (GOD) is immobilized onto the resulting film to construct a glucose biosensor through self-assembly. The resulting modified electrode surfaces are characterized with both AFM and cyclic voltammetry. Effects of chitosan and HAuCl(4) concentration in the mixture together with the deposition time and the applied voltage on the amperometric response of the biosensor are also investigated. The linear range of the glucose biosensor is from 5.0 x 10(-5) approximately 1.30 x 10(-3) M with a Michaelis-Menten constant of 3.5 mM and a detection limit of about 13 microM.     

基于Dy_2(MoO_4)_3-AuNPs复合纳米材料的葡萄糖生物传感器

采用水热法合成了纳米材料钼酸镝[Dy_2(MoO_4)_3],并制备了Dy_2(MoO_4)_3-AuNPs复合材料,利用该复合材料固定葡萄糖氧化酶(GOD)构建了葡萄糖生物传感器.通过透射电子显微镜(TEM)、紫外-可见光谱(UV-Vis)和能谱分析(EDS)等手段对所制备的材料进行了表征,并利用电化学阻抗谱(EIS)和循环伏安(CV)曲线研究了该传感器的电化学性能.结果表明,Dy_2(MoO_4)_3-AuNPs复合材料具有较好的生物相容性,能增强固定化的GOD的生物活性,并促进GOD在电极表面的电子传递速率;该传感器在葡萄糖浓度为0.01~1.0 mmol/L范围内葡萄糖浓度与响应电流呈较好的线性关系,最低检出限为3.33μmol/L(S/N=3),该生物传感器还具有较好的稳定性和重现性.     

基于纳米金和硫堇固定酶的过氧化氢生物传感器

在铂电极上自组装一层纳米金(GNs), 构建负电荷的界面, 然后通过金-硫、金-氮共价键合作用和静电吸附作用自组装一层阳离子电子媒介体硫堇(Thio). 再以同样的作用自组装一层GNs和辣根过氧化酶(HRP)的混合物, 最后在电极最外层滴加一层疏水性聚合物壳聚糖(Chit), 由此制备了一种新型的过氧化氢生物传感器. 研究了工作电位、检测底液pH、温度对响应电流的影响, 以及GNs和HRP之间的相互作用, 探讨了传感器的表面形态、交流阻抗、重现性和稳定性. 该传感器的酶催化反应活化能为12.4 kJ/mol, 表观米氏常数为6.5×10^－4 mo/L, 在优化的实验条件下, 所研制的传感器对H₂O₂的线性范围为5.6×10^－5～2.6×10^－3 mol/L, 检出限为1.5×10^－5 mol/L. 应用此方法制备了HRP和葡萄糖氧化酶(GOD)双酶体系葡萄糖生物传感器, 并应用于实验样品葡萄糖含量的测定.     

Direct Electron Communication Between Glucose Oxidase and Carbon Electrode Covered with Polypyrrole

IntroductionDirectelectrochemistryofenzymeshasarousedincreasinginterestofmanyresearchersasitisapreferablewayforproducingarealreagent1essbiosensor.Glucoseoxidase(GOD),beingaflavoprotein,iswell-knownduetoitswidespreaduseinthebiosensors'Recently,agreatnumberofpeoplehaveat-temptedtoachievedirectelectrontransferbetweenGODandvariouselec-trodes[l-19].Szucselal.determinedtheshapeandsizeoftheGODmoleculead-sorbedonagoldelectrodebyel1ipsometry['jandexamineddirectelectrontrans-ferbetweentheadsorbedenz…     

介孔碳修饰玻碳电极上葡萄糖氧化酶的直接电化学

使用简单的方法将葡萄糖氧化酶(GOD)固定在介孔碳(Mesoporous Carbon)修饰的玻碳电极(GCE)表面.循环伏安测试表明:修饰电极上的GOD在0.1mol/L磷酸缓冲溶液(PBS)(pH=7.1)中发生了准可逆的氧化还原反应,其克式量电位为-0.4294 V,并且该电化学反应包含有两电子两质子的传递.在氮气饱和的情况下,以羧基二茂铁作为电子传递中介体,GOD能将葡萄糖彻底催化氧化,可见介孔碳修饰电极上的GOD保持了其生物学活性.     

镀金和碳纳米管修饰金电极上吸附态葡萄糖氧化酶比活性的EQCM研究

采用石英晶体微天平(EQCM)技术监测了裸金电极、镀金和碳纳米管修饰金电极上葡萄糖氧化酶(GOD)的吸附过程. 通过EQCM测量吸附固定的GOD质量, 并实时检测酶反应产物H2O2的氧化电量, 求算了各表面上吸附态GOD的比活性(ESAi). 结果表明, 各表面上均可吸附一定的GOD, 且吸附态GOD均有一定的酶活性; 修饰CNTs可增大酶吸附量和酶电极对葡萄糖的响应电流, 但ESAi随CNTs修饰量的增大而降低; Au电极上电镀金后, 酶吸附量和酶电极对葡萄糖的响应电流亦增大, 但ESAi与裸金电极上的基本一致.     

A Comparison of a Nanostructured Enzymeless Au/Fe2O3/MWCNTs/GCE Electrode and a GOx Modified One in Electrocatalytic Detection of Glucose

Acid functionalized multi‐walled carbon nanotubes (f‐MWCNTs) were decorated with Au and Fe₂O₃ nanoparticles (FeONPs) and deposited on glassy carbon electrode (GCE). The resulting hybrid Au/Fe₂O₃/f‐MWCNTs/GCE electrode and the one further modified by glucose oxidase were compared for detection of glucose. FeONPs and Au were deposited on the f‐MWCNTs by sonication‐assisted precipitation and deposition‐precipitation methods, respectively. The morphology and structure of the samples were characterized by transmission electron microscopy, scanning electron microscopy, X‐ray diffraction and Raman spectroscopy. A uniform distribution of FeONPs with an average size of 5 nm increased the surface area of functionalized nanotubes from 39 to 50 m²/g. The electrocatalytic glucose detection on the modified electrodes was evaluated using cyclic voltammetry and chronoamperometry in 0.1 M phosphate buffer solution at pH 7.0. The non‐enzymatic and enzymatic electrodes show sensitivity of 512.4 and 921.4 mA/mM.cm² and detection limit of 1.7 and 0.9 mM, respectively. The enzymatic and enzymeless electrodes retained more than 70 % and 80 % of their cathodic faradic current after 70 days, respectively. The sensing mechanism of the non‐enzymatic biosensor is described through the reaction of glucose with iron (III) ions, while in the case of enzymatic electrode, glucose is oxidized by glucose oxidase.     

Ceramic Carbon/Polypyrrole Materials for the Construction of Bienzymatic Amperometric Biosensor for Glucose

Amperometric enzymatic biosensors have high selectivity and simplicity in use. It has advantages over other analytical methods in biochemistry, pharmacology, so it evokes strong interests1,2. Generally, the detection mode involved in oxidase based biosensors is often based on the electrochemical detection of hydrogen peroxide directly3,4. However the direct oxidation of hydrogen peroxide requires a relative high working potential (exceeding ca. 0.6 V vs. SCE), at which many biological sub…     

基于壳聚糖-纳米金/纳米普鲁士蓝/L-半胱氨酸修饰的 葡萄糖传感器的研究

在金电极表面修饰一层L-半胱氨酸,再利用静电吸附作用固定纳米普鲁士蓝(nano-PB),然后利用壳聚糖-纳米金复合膜将葡萄糖氧化酶(GOD)固定于修饰电极表面,制成新型的葡萄糖传感器.通过交流阻抗技术,循环伏安法和计时电流法考察了电极的电化学特性.在优化的实验条件下,该传感器在葡萄糖浓度为3.0×10-6～1.0×10-3 mol/L范围内有线性响应,检测下限为1.6×10-6 mol/L.此外该传感器具有响应快、稳定性好和选择性良好的特点,能有效排除常见干扰物质如抗坏血酸、尿酸等对测定的影响.     

Size-dependence enhancement in electrocatalytic activity of NiHCF-gold nanocomposite: potential application in electrochemical sensing

A nanocomposite of nickel hexacyanoferrate (NiHCF) was made with gold nanoparticles (AuNPs) of two different sizes (20 and 80 nm as AuNP(red) and AuNP(blue) respectively), synthesized via 3-glycidoxypropyltrimethoxysilane mediated reduction of 3-aminopropyltrimethoxysilane treated gold chloride and characterized by scanning electron microscopy and UV-VIS spectroscopy. The size of AuNPs was found to influence the two pairs of reversible voltammetric peaks of cation rich and cation deficient NiHCF. Such influence was identified from cyclic voltammetry of nanocomposite modified electrodes and applications during electrochemical sensing of two different analytes hydrazine and glutathione (GSH). Electrochemical sensing of hydrazine was based on cyclic voltammetry and differential pulse voltammetry (DPV) found as a function of sodium deficient NiHCF and was greatly amplified with increasing AuNPs nanogeometry. NiHCF alone is not an efficient electrode material for GSH analysis at the level required, however, the presence of AuNPs introduces size dependent sensitive and selective detection of GSH. GSH sensing based on linear sweep voltammetry (LSV) was found to be mediated by the potassium rich form of NiHCF redox couple in the presence of AuNPs. The results justified electrochemical detection of these analytes based on a mediated mechanism and support the role of AuNPs for facilitated electrochemical activity of NiHCF based systems as a function of nanogeometry.     

Bienzymatic amperometric biosensor for glucose based on polypyrrole/ceramic carbon as electrode material

A novel amperometric biosensor utilizing two enzymes, glucose oxidase (GOD) and horseradish peroxidase (HRP), was developed for the cathodic detection of glucose. The glucose biosensor was constructed by electrochemical formation of a polypyrrole (PPy) membrane in the presence of GOD on the surface of a HRP-modified sol-gel derived-mediated ceramic carbon electrode. Ferrocenecarboxylic acid (FCA) was used as mediator to transfer electron between enzyme and electrode. In the hetero-bilayer configuration of electrode, all enzymes were well immobilized in electrode matrices and showed favorable enzymatic activities. The amperometric detection of glucose was carried out at +0.16 V (versus saturated calomel reference electrode (SCE)) in 0.1 M phosphate buffer solution (pH 6.9) with a linear response range between 8.0×10⁻⁵ and 1.3×10⁻³ M glucose. The biosensor showed a good suppression of interference in the amperometric detection.     

纳米聚苯胺修饰石墨电极的葡萄糖双酶传感器

用循环伏安法在石墨电极上制得纳米纤维聚苯胺, 并在其上固定葡萄糖氧化酶(GOD)和辣根过氧化物酶(HRP)制备葡萄糖双酶传感器. 用交流阻抗、SEM等技术对其进行表征; 考察了各种因素对双酶电极响应电流的影响以及双酶电极的稳定性. 该传感器对葡萄糖响应电流的测定在0.05 V(vs SCE)下进行, 有效避免了电活性物质的影响, 线性响应范围为0.05-2.0 mmol·L-1.