基于金属有机骨架的非酶葡萄糖电化学传感器

葡萄糖的快速有效检测在维持人体健康、疾病控制与诊断、生物科学和食品科学等方面具有重要意义.基于金属有机骨架(MOFs)的催化活性和比表面积大等特点,MOFs已被成功开发为非酶葡萄糖电化学传感器.本文综述了基于非改性MOFs、纳米金属粒子掺杂MOFs、金属及金属氧化物核@MOFs、碳纳米材料@MOFs、核-壳MOFs在检...     

纳米金属铜与纳米氧化锌之间相互作用的EPR和XPS研究

由于纳米材料独特的表面效应、电子效应及量子尺寸效应 ,已被广泛应用于各个领域 .有关纳米材料研究的报道很多 [1～ 7] ,大部分是关于纳米材料的制备[1～ 4 ] 及其特性研究 .对于纳米金属及纳米氧化物之间相互作用的研究迄今尚未见报道 .本文采用超声分散和机械研磨法物理混合纳米金属铜粉和纳米氧化锌 ,借助 EPR和 XPS技术对样品进行了表征 ,发现混合体系出现了 Cu2 + 的顺磁信号 ,Zn L3M4 5M4 5俄歇动能和 O1s的电子结合能亦发生了变化 ,表明纳米 Cu0 和纳米 Zn O之间存在相互作用 ,作用形式为 Cu— O—Zn.1　实验部分1 .1　样品…     

二次刻蚀聚酰亚胺负载CuxO纳米复合物薄膜电极用于葡萄糖的快速测定

本文采用激光刻蚀聚酰亚胺薄膜为载体, 浸泡吸附铜离子后经过二次刻蚀还原得到含有Cu(0)、Cu(I)和Cu(II)的纳米复合物薄膜电极(SLEPI/Cu_xO-FE). 通过表征可知,SLEPI/Cu_xO-FE具有大比表面积、丰富的活性位点以及良好的电催化性能. 实验结果表明,该电极对葡萄糖具有良好的电化学响应,并具有较好的稳定性和重现性,有望应用于葡萄糖的低成本检测.     

Gold Microelectrodes Decorated by Spike-Like Nanostructures as a Promising Non-Enzymatic Glucose Sensor

Gold microelectrodes modified via easy method by gold nanostructures were studied as an ideal substrate for non-enzymatic glucose detection. The results confirmed that spike-like nanostructure displays the best electrocatalytic activity because of higher amount of edges. Results prove that modified electrode is able to detect glucose in two linear ranges from 100–500 μM and 0.5–30 mM, with limit of detection (48 μM), high sensitivities for both linear ranges (1.7 μA/mM and 2.4 μA/mM), and good stability. In addition, modified electrodes were able to detect glucose in blood serum. This work demonstrates glucose detection on miniaturised system.     

The Rapid and Practical Route to Cu@PCR Sensor: Modification of Copper Nanoparticles Upon Conducting Polymer for a Sensitive Non-Enzymatic Glucose Sensor

In this work, rapid, sensitive, practical, and economical strategy for non-enzymatic glucose sensor has been reported based on a modification of copper nanoparticles upon conducting polymer with high surface area (Cu@PCR). Firstly, PCR conducting polymer electrode (PCR) has been successfully fabricated by electrochemical polymerization of a specially synthesized and characterized star-shaped carbazole derivative. Then copper nanoparticles have been successfully electrodeposited on the PCR as a practical method with cyclic voltammetry. The morphologies of the synthesized materials have been characterized by scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) measurements. The Cu@PCR sensor platform has been displayed a synergistic effect of high catalytical properties of copper nanoparticles and high electroactive properties of PCR towards the glucose oxidation in alkaline medium. The Cu@PCR sensor platform has shown high sensitivity of 847 μAmM⁻¹cm⁻², good stability (10 weeks), a low detection limit of 0.043 μM, and a fast response of 3 s for the non-enzymatic electrochemical detection of glucose. This organic−inorganic hybrid composite sensor is a promising candidate for the fabrication of a highly sensitive and rapid glucose-sensing with the simple preparation procedure and use of a low-cost precursor.     

无酶葡萄糖检测的研究进展

本文主要介绍了各种无酶葡萄糖的检测方法。 相对于酶法,该方法克服了由于酶本身固有的属性而导致的在固定化过程中不稳定易失活的缺点,具有较好的重现性、稳定性以及抗干扰能力。     

纳米ZnO增强葡萄糖生物传感器的制备和应用

为提高葡萄糖生物传感器的灵敏度,以纳米ZnO与聚乙烯醇缩丁醛(PVB)构成复合固定酶膜基质,采用溶胶-凝胶法固定葡萄糖氧化酶(GOD),用戊二醛进行交联,制成葡萄糖生物传感器。实验结果表明,GOD可牢固地固定在电极表面,在相同葡萄糖浓度下,加入纳米颗粒的电极的电流响应值比未加颗粒的高约100倍,电极重复使用46次后电流响应值仅下降到初始的70%。电极制备方法简单,易于操作。同时对温度、溶液pH值以及溶剂对电极的影响进行了研究,获得了最优的实验条件。     

Heterostructural NiCo2O4 Nanocomposites for Nonenzymatic Electrochemical Glucose Sensing

Hierarchical nanocomposites consisting of NiCo₂O₄ nanorods and NiCo₂O₄ nanoparticles through a straightforward two-step hydrothermal process was employed as a working electrode to examine the electrochemical behavior of glucose. The NiCo₂O₄@NiCo₂O₄ heterostructures was confirmed by the scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffractometer (XRD), X-ray photoelectron spectroscopy (XPS) and electrochemistry analysis. Results indicated that glucose is electrochemically oxidized with improved sensitivity at the NiCo₂O₄@NiCo₂O₄ sensor, compared to NiCo₂O₄ sensors. Analytical parameters such as the optimal potential (0.45 V), linear range from 0.4 μM to 5.2 mM, limit of detection (1.1 μΜ) (S/N=3), stability and repeatability (2.7 %) demonstrate the suitability of the prepared sensor for glucose analysis. Moreover, the proposed sensor could be used for actual samples analysis in complex matrices.     

酶法合成的葡萄糖氧化酶-纳米金复合物的直接电化学与生物传感

将NaAuCl₄、葡萄糖氧化酶（GOx）和葡萄糖混合,借一步酶促反应制得吸附GOx的金纳米颗粒（AuNPs）,再通过滴干修饰法研制了Nafion/GOx-AuNPs修饰的玻碳（GC）电极,并考察了该酶电极上GOx的直接电化学和生物传感性能. 这种酶法合成的GOx-AuNPs复合物有良好的酶直接电化学活性,也保持了GOx的生物活性,似可归因于酶法合成的纳米金更接近酶氧化还原活性中心的缘故. 该酶电极在-0.4 V（vs. SCE）电位下,其稳态电流下降与葡萄糖浓度（0.5 4 mmol·L^-1）成正比,检测下限0.2 mol·L^-1.     

纳米氧化锌的机械力化学表面改性

采用机械力化学表面改性工艺,以硬脂酸为改性剂,在气流粉碎机中对纳米氧化锌进行解团聚和表面改性,并借助SEM、XRD、FF—IR和XPS对改性前后的氧化锌粉体进行结构表征．结果表明：硬脂酸分子化学键合在氧化锌表面．改性前后氧化锌的晶体结构相同,其颗粒的团聚性降低,二次粒径明显减小．通过测定改性样品的活化指数和亲油化度,选择最佳的改性剂用量为氧化锌质量的10％,氧化锌表面亲油疏水,在有机溶剂中有较好的分散性．     

Novel Sn Doped Co3O4 Thin Film for Nonenzymatic Glucose Bio‐Sensor and Fuel Cell

A facile chemical solution deposition via two‐step spin coating technique was used to fabricate nano‐particulate novel Sn doped Co₃O₄ thin film for glucose sensor and fuel cell applications. Substitution of Sn into Co₃O₄ host lattice lead to a remarkable increase in the electrocatalytic activity of the Co₃O₄ electrode material. Film thickness played a significant role in enhancing the charge transferability of the electrode as was observed from electrochemical impedance spectroscopy (EIS). The best sensor exhibited two wide linear response ranges (2 μM up to ∼0.5 mM and 0.6 mM up to ∼5.5 mM respectively) with sensitivities of 921 and 265 μA cm⁻² mM⁻¹ respectively and low limit of detection of 100 nM (S/N=3). The sensor was very selective towards glucose in the presence of various interference and showed long term stability. Moreover, the developed thin film modified electrode could generate one electron current in nonenzymatic fuel cell setup at room temperature.     

锰基配位聚合物的简易合成、结构及其在葡萄糖电化学传感中的应用

利用刚性配体6-（3-吡啶基）间苯二甲酸（H₂PIAD）,制备了一种基于Mn （Ⅱ）的配位聚合物{[Mn （PIAD）（DMF）]·H₂O}_n（1）。采用后合成Ag纳米颗粒的策略制备了复合材料（Ag@1）以提高葡萄糖传感的电催化活性。在优化的外加电位下,通过计时电流法评估了Ag@1修饰的玻碳电极（GCE）的电催化性能。配位聚合物1为在其表面的Ag纳米颗粒均匀分布提供了固定基质,而且Ag@1传感器可以最大限度地发挥Ag与1结合对葡萄糖氧化的电催化协同效应。结果表明,Ag@1修饰的GCE对葡萄糖的检测性能良好,检出限低（6.36 μmol·L^-1）,选择性和灵敏度好（166.71 μA·L·mmol^-1·cm^-2）。     

Non-Basic Solution Routes to Prepare ZnO Nanoparticles

Nanocrystalline ZnO particles were prepared from alcoholic solutions of zinc acetate dihydrate without using base such as NaOH or LiOH through a colloid process carried out at a low temperature of 60°C. A comparative study of chemical reactions from zinc acetate dihydrate to ZnO was made using different types of monool solvents, i.e. methanol, ethanol, and 2-methoxyethanol. It was revealed that layered hydroxide zinc acetate was formed as an intermediate and its transformation into ZnO was a key reaction step in any of the solutions. Reaction time necessary for the precipitation of ZnO was greatly influenced by the solvents used. Methanol was useful for the preparation of the ZnO nanoparticles, which were chemically pure in terms of cation impurities and exhibited green photoluminescence by the ultraviolet excitation.     

纳米金胶增强葡萄糖生物传感器的构建

将纳米金胶(AuNPs)和羟基磷灰石(HAp)按一定比例混合制备了新型复合膜用于葡萄糖氧化酶(GOD)的固定,构建了高灵敏的葡萄糖传感器。由于纳米金胶的存在,葡萄糖氧化酶的直接电化学性质得以增强,在去除氧气的PBS(pH 7.0)介质中,固定在复合膜内的GOD表现出一对良好的氧化还原峰。在饱和氧气条件下,当加入一定量的葡萄糖时,由于GOD催化葡萄糖氧化消耗溶液中的溶解氧,-0.8 V处溶解氧的还原峰电流降低,且峰电流降低的量与葡萄糖浓度在0.02～1.62 mmol/L范围内呈线性相关,检出限为5.0μmol/L,检测灵敏度达9.91 mA.mol-1.L,可实现对葡萄糖的快速检测。     

Controlled Variable Oxidative Doping of Individual Organometallic Nanoparticles

The charging and controlled oxidative doping of single organometallic ferrocene nanoparticles is reported in aqueous sodium tetrafluoroborate using the nano‐impacts method. It is shown that ferrocene nanoparticles of approximately 105 nm diameter are essentially quantitatively oxidatively doped with the uptake of one tetrafluoroborate anion per ferrocene molecule at suitably high overpotentials. By using lower potentials, it is possible to achieve low doping levels of single nanoparticles in a controlled manner.     

不同形貌ZnO纳米粒子的超声化学法制备与表征

One-dimensional ZnO nanorods and shuttle-like ZnO nanoparticles have been successfully achieved by ultrasonic irradiation of Zn (CH3COO)2 aqueous solution and Zn-NH3 complexcs solution. The obtained ZnO nanoparticles have been characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM) and selected area electronic diffraction (SAED). And the formative mechanism of the prepared different morphological ZnO nanoparticles is also discussed under ultrasonic irradiation.     

Low-applied Potential Non-enzymatic Glucose Sensor Based on Ultrathin 2-D CuS Nanowall Arrays

The 2-D nanostructure, due to unprecedented physical, electronic, and chemical properties, was widely dedicated to the zooms of electrocatalysis, batteries, supercapacitors, solar cells, photocatalysis and sensing platforms. Herein, we reported a sort of low-applied potential non-enzymatic glucose sensor, which used ultrathin 2-D CuS nanowall arrays (CuS-NWAs) fabricated directly onto fluorine-doped tin oxide glass by potentiostatically deposition approach. Meaningfully, the potentiostatical-deposition time can control precisely the frame of 2-D CuS-NWAs on size and thickness and assist to ferret out the growing mechanization by analyzing the copper valence. Then, CuS-NWAs-based non-enzymatic glucose sensor presented the high sensitivity (2610 μA mM⁻¹ cm⁻²), a low detection of 17 nM, fast respond time (1.5–6.2 s) and low detection limits (2.6–17.7 nM, S/N=3) regardless of an applied potential as low as 0.33 V (vs. Ag/AgCl), attributed to that the 2-D CuS-NWAs offer large active area with numerous exposed active points, a low-resistance electron-shuttling passage and door-opened glucose-diffusion channel. Additionally, it was found that the sensitivity of CuS-NWAs-based non-enzymatic glucose sensors can be optimized by altering electrodeposition duration for CuS-NWAs growth. Confirmedly, the 2-D CuS-NWAs can be promised as a new system for high-performance electrochemical sensors with excellent properties of selectivity, stability and reproducibility.     

单根ZnO纳米线的室温气敏特性

利用改进的CVD法制备了(002)面取向生长的ZnO纳米线, 通过光刻/剥离的自下而上的组装技术制备了基于单根ZnO纳米线的气敏元件, 其中的ZnO纳米线直径为50-300 nm, 有效长度为2-10 μm. 测试表明在室温条件下, 元件对浓度为500 μL·L-1的氧气和乙醇的灵敏度可以分别达到1.3 和1.2, 而气敏响应时间分别为10 和5 s, 由于单根纳米线的一维小尺寸结构加剧了电流的自加热效应, 因此元件在外界环境为室温的条件下的灵敏度才略有提高.     

Preparation of ZnO Nanoparticles: Structural Study of the Molecular Precursor

The structure of zinc acetate derived precursor currently used in the sol-gel synthesis of ZnO nanoparticles is described. The reaction products obtained before and after reflux of ethanolic zinc acetate solution have been studied by UV-Vis, photoluminescence, FTIR and EXAFS at the Zn K edge. EXAFS results evidence for both precursor solutions a change from the octahedral coordination sphere of oxygen atoms characteristic of the solid zinc acetate dihydrate compound into a four-fold environment. The EXAFS spectra of precursor solutions can be satisfactorily reproduced using the molecular structure reported for Zn₄O(Ac)₆ (Ac = COOCH₃). UV-Vis and FTIR measurements are also in agreement with the formation of this oligomeric precursor. The structural modification is more pronounced after reflux at 80°C, because the increase of the Zn₄O(Ac)₆ amount and the formation of nearly 3.0 nm sized ZnO nanoparticle.