电化学石英晶体微天平及其应用

本文介绍了ＥＱＣＭ的原理及其应用，探讨了ＥＱＣＭ在生物大分子，纳米技术方面的应用，详细介绍了ＥＱＣＭ在气味检测，金属电沉积、药物分析等方面研究的优点和ＥＱＣＭ的发展前景。     

电化学石英晶体微天平研究普鲁士蓝修饰电极

石英晶体徽天平(Quartz Crystal Microbalance,简称QCM)是一种非常灵敏的质量传感器,其检测能力可达ng级。QCM在化学中的早期应用是检测大气中的徽量成分,目前仍较活跃。由于石英压电晶体浸入溶液后在晶体/溶液界面存在较大的能量损失而不能够稳定振荡,致使QCM的应用较长时间局限于气相。八十年代初石英压电晶体在液相中的振荡终获成功,开辟了QCM应用的一个全新领域。液相中振荡成功后,QCM很快应用于电化学研究。目前已发展成为一种全新的电化学传感器——电化学石英晶体微天平(EQCM),并已用于金属电沉积、电化学腐蚀、电分析等方面的研究。     

石英晶体微天平用于免疫球蛋白M免疫反应的动力学研究

在镀银电极的压电石英晶体表面涂覆甲基丙烯酸甲酯－甲基丙烯酸羟乙酯共聚物涂层，经ＣＮＢｒ活化后固定抗体，用石英晶体微天平技术监测ＩｇＭ抗原在压电石英晶体上的吸附与解吸过程，研究了免疫反应体系ＩｇＭ－抗人ＩｇＭ的反应动力学．结果表明：ＩｇＭ在压电石英晶体上的键合行为很好地符合Ｌａｎｇｍｕｉｒ吸附方程，免疫反应的结合常数Ｋａｓｓ为７．１０×１０￣７（ｍｏｌ／Ｌ）￣（－１）．在抗原过量情况下为一级反应。计算了ＩｇＭ免疫反应的活化能Ｅａ和不同温度下的反应速率常数ｋｆ．     

石英晶体微天平（QCM）及其在电化学研究中的应用

本文文献综述近年来发展起来的石英晶体微天平(QCM)技术的理论、实验方法和它在电化学研究中应用的概况。     

电化学石英晶体微天平的近期应用进展

本文对近几年来电化学石英晶体微天平（EQCM）在吸附,膜的形成,腐蚀和电沉积等方面的应用进行了概述,并对其应用现状和前景进行了分析。     

电化学石英晶体微天平应用研究和背景扣除

基于用循环伏安法研究非理想可逆体系时,电极本身的氧化峰电量与还原峰电量存在一比值。据此建立了一种用于电化学石英晶体微天平应用研究的背景扣除新方法。用这种方法研究了腺嘌呤、腺苷、腺苷一磷酸在金电极上的电化学氧化行为。结果表明:3种活性分子均能在1.2V左右氧化,对应的氧化电流大小顺序为:腺嘌呤>腺苷>腺苷一磷酸,氧化过程的电子转移数为6。     

石英晶体微天平在高分子科学中的应用

固/液界面上高分子的行为直接影响着界面的物理和化学性质.对于高分子在界面的动态行为,由于缺乏有效的手段,检测一直十分困难.最近,一种频率-耗散联用型石英晶体微天平(QCM-D)问世,它能够同时检测固/液界面上有关高分子质量和结构的变化,因而可应用于界面高分子研究的多个方面.本文介绍石英晶体微天平的基本原理,并综述作者实验室最近几年利用QCM-D开展的若干工作,包括固/液界面上高分子链的构象变化,固/液界面上高分子的吸附,高分子降解动力学和聚电解质的"层层组装"等方面.     

石英晶体微天平的新进展

石英晶体微天平（quartz crystal microbalance,QCM）是一种对界面变化敏感的仪器,它已经在物理、化学、生物学、药物学、临床医学、环境科学等学科的界面问题研究中得到了一定的应用.然而,QCM在液相下的应用和推广一直受限于QCM数据定量解释的困难.为此,科研工作者发展了多种高级的QCM,比如带阻抗分析功能的QCM（impedance QCM,i-QCM）或带能量耗散监测功能的QCM（QCM with dissipation,QCM-D）,同时还发展了许多相应的理论模型.但是,对于多数生物、化学工作者来说,这些理论过于复杂.这极大地限制了QCM的推广和潜力发挥.本文以我们小组在QCM方面的研究工作为线索,对已报道的分析方法、模型和方程按5类应用条件进行了整理,给出了明确的界定标准：它们是：1,固-气界面;2,牛顿流体;3,固-液界面的薄膜;4,固-液界面厚膜;5,固-液界面超厚膜.对于每一类情况,我们将用通俗易懂的语言描述如何对QCM数据进行简化却又保证研究精度需要的定量分析.对于液态环境下的QCM数据的分析,我们着重介绍了＂固化水层＂模型,该模型允许QCM在一定的条件下成为一把＂分子尺＂,工作范围从几个纳米到数百纳米.该分子尺在多个创新界面问题研究中得到很好的应用.最后,我们从理论上分析了QCM作为生物传感器的先天缺陷--因基于面均质量检测的原理,QCM技术对溶液中蛋白的检测下限仅在1μg mL-1数量级.进一步,我们探索了QCM的发展方向和潜在应用领域,希望籍此能进一步推广QCM在各个学科界面问题中的研究应用.     

石英晶体微天平传感器及其在生物检测中应用的研究进展

石英晶体微天平(Quartz crystal microbalance,QCM)是一种具有灵敏度高、免标记、可实时在线检测等优点的重要分析工具。在生物检测领域,QCM与多种信号放大方法相结合,广泛应用于对生物分子的高灵敏检测。新型耗散型QCM(QCM-D)通过对薄膜厚度、粘弹性等的研究,主要用于考察生物分子的吸附分离、构型变化等微观过程。本文主要阐述了QCM及QCM-D生物传感器的构建及其在DNA、蛋白质、细胞和微生物检测中的研究进展。     

压电晶体微天平阵列传感器识别毒剂的研究

压电晶体微天平(QCM)阵列传感器在毒剂侦检领域具有广泛的应用前景。本研究建立了QCM阵列传感器毒剂检测系统,以氢键酸性共聚硅氧烷(BSP3)、聚表氯醇(PECH)和乙基纤维素(ECEL)为膜材料制备了对毒剂敏感的QCM阵列传感器,对沙林、芥子气、甲基膦酸二甲酯进行了定量检测,并结合模式识别方法对检测结果进行了分析处理,识别率达到98%以上,为探索QCM阵列传感器对毒剂的定性定量分析提供了方法依据。     

石英晶体微天平(QCM)及其在大气腐蚀研究中的应用

从石英晶体微天平的基本原理出发,结合作者的文献调查及近期利用石英晶体微天平对大气腐蚀的研究结果,综述了石英晶体微天平在金属大气腐蚀研究中的重要作用,指出石英晶体微天平在金属大气腐蚀研究中的优点,存在的问题和相应的解决办法。     

用石英晶体微天平研究表面活性剂在银固态表面上的动态吸附

吸附是表面活性剂的一个重要特征.迄今用于原位监测表面活性剂在固体表面上吸附重量变化的方法尚不多见.近年来压电石英晶体作为一种高灵敏的质量传感器(石英晶体微天平)已被用于大气和溶液中多种微量成分的监测.用石英晶体微天平研究I~-、Br~-和表面活性剂在金电极上的吸附行为亦有报道.本文研究了十六烷基三甲基溴化铵(CTAB)、十二烷基磺酸钠(SDSO)、十二烷基硫酸钠(SDS)在银固态表面上的吸附平衡动力学特性及其吸附机制.     

Quartz Crystal Microbalance monitoring the real-time binding of lectin with carbohydrate with high and low molecular mass

A Quartz Crystal Microbalance (QCM) was used to monitor the mass changes on a quartz crystal surface containing immobilized lectins that interacted with carbohydrates. The strategy for lectin immobilization was developed on the basis of a multilayer system composed of Au–cystamine–glutaraldehyde–lectin. Each step of the immobilization procedure was confirmed by FTIR analysis. The system was used to study the interactions of Concanavalin A (ConA) with maltose and Jacalin with Fetuin. The real-time binding of different concentrations of carbohydrate to the immobilized lectin was monitored by means of QCM measurements and the data obtained allowed for the construction of Langmuir isotherm curves. The association constants determined for the specific interactions analyzed here were (6.4 ± 0.2) × 10⁴ M^− 1 for Jacalin–Fetuin and (4.5 ± 0.1) × 10² M^− 1 for ConA–maltose. These results indicate that the QCM constitutes a suitable method for the analysis of lectin–carbohydrate interactions, even when assaying low molecular mass ligands such as disaccharides.     

电化学石英晶体微天平对银电极氧化还原过程的研究

建立了电化学石英晶体微天平（ＥＱＣＭ）－循环伏安联用技术，并以此研究了碱性溶液中银的氧化还原行为。在伏安扫描的同时，现场记录电极表面的质量变化，得到与电流－电势曲线相对应的质量－电势谱。结果表明本体Ａｇ２Ｏ形成之前银溶解和生成表面化合物的过程共存，阴极方向的氧化峰确定是ＡｇＯ的继续生成。在ＡｇＯ还原为Ａｇ２Ｏ的阶段观察到了异常的质量变化，并进行了讨论。     

Determination of the Boron/Lead Ratio in Ceramic Materials Based on Electrochemical Quartz Crystal Microbalance

A method for quantitatively determining the relationship boron/lead in ceramic materials is presented. It is based on the attachment of microsamples of ceramic frits to an electrochemical quartz crystal microbalance (EQCM). After a reductive deposition step in the ?0.25 to ?0.85 V (vs. AgCl/Ag) potential range, well‐defined stripping peaks are recorded in 0.10 M NaCl plus 0.10 M mannitol. The deposition of boron and lead from suspensions of solid materials, and its subsequent oxidative dissolution can be monitorized at the EQCM. The quotient between the maximum mass gain and the corresponding charge passed enables for a direct quantitation of the boron/lead molar ratio in ceramic materials. Addition methods based on the EQCM examination of i) sample plus lead white (2PbCO₃.Pb(OH)₂) and ii) sample plus Li₂B₄O₇ mixtures are also presented. Results for boron‐containing ceramic frits are in excellent agreement with those obtained by reference methods.     

Rapid Detection of Staphylococcal Enterotoxin B by Two-Dimensional Molecularly Imprinted Film-Coated Quartz Crystal Microbalance

We fabricated a two-dimensional (2D) molecularly imprinted sol-gel thin film-coated quartz crystal microbalance (QCM) for the rapid detection of staphylococcal enterotoxin B (SEB) by combining organosilanes and the template protein SEB on the surface of piezoelectric quartz crystal (PQC) Au-electrode by in-situ immobilization. The detection process was monitored by the QCM's frequency shift (Δf). The working range of this method was 1.0 × 10^?1–1.0 × 10³ µg/mL. The detection limit was 6.1 ng/mL, which was lower than that of the PQC immunosensor, and the detection period was within 0.5 h. The reproducibility of the imprinted film-coated QCM was satisfactory due to no significant statistical difference (P > 0.05) in the rapid detection of SEB between intra- and inter-batch. The selectivity of the imprinted sol-gel film showed that it could discriminate the template molecule from its analogues and other guest molecules. Compared with immunochip, the imprinted film-coated QCM is more advantageous in terms of simplicity, rapidity, low cost, and sensitivity. Moreover, in real sample analysis, the recoveries of this method were 89.4–106.63%, which can be considered a favorable and applicable method for the rapid determination of SEB in real samples.     

石英微天平定量分析纳米Pd/TiO2对农药的吸附与降解

采用压电石英微天平(QCM)技术研究了有机农药甲基对硫磷在经钯(palladium,Pa)掺杂和软脂酸(palmic acid)改性前后的纳米TiO2上的吸附和降解行为。研究表明Pd和PA均能提高纳米TiO2对非极性有机农药的吸附量,复合纳米TiO2和Pd/TiO2的最大吸附量Г∞分别为6.18×10-4mol/g和7.54×10-4mol/g,吸附常数k分别为5.72×103L/mol和1.79×103L/mol。光降解和毒力实验结果表明复合纳米TiO2和Pd/TiO2农药制剂可在太阳光照下自行降解,在农作物体内的残留期大大缩短,且复合纳米TiO2和Pd/TiO2农药制剂的毒力有明显的提高,5%的纳米TiO2和Pd/TiO2乳液的毒力分别是95%原药毒力的1.68倍和2.19倍。     

Improving the Sensitivity of a Quartz Crystal Microbalance for Biosensing by Using Porous Gold

 A quartz crystal microbalance can be used as a biosensor if biological receptor molecules (ligands) are attached to the crystal. To improve the sensitivity, the surface area of the gold electrodes on the crystal was increased by rendering the electrodes porous. This increased the response up to a factor of 3. A protein model system with human anti-myoglobin as ligand and sheep skeletal myoglobin at different concentrations as analyte was used. The quartz crystal was mounted in a flow-cell, where immobilisation, binding and regeneration of the surface were carried out. The kinetics of the model system was monitored under various experimental conditions. Received February 2, 2000. Revision June 30, 2000.     

Applying the Quartz Crystal Microbalance Technique to Detect the Epithelial Cell Tight Junction Integrality of Caco-2 Cells

This paper describes a method that utilizes the quartz crystal microbalance (QCM) technique to measure the tight junction of the Caco-2 cell. The Caco-2 cells are placed on the QCM surface for cell growth and tight junction measurements. We found that the QCM resonance frequency changes less when a better tight cell junction is formed. The quantity of QCM frequency change is less than 100 Hz as the tight junction cell integrality is completed up to 15 days. The QCM and traditional detection system transepithelial electrical resistance were similar as the cell growth affects the two systems over time.