Immunodetection by quartz crystal microbalance

Biodetection is one of the most important challenges for the twenty-first century: many fields are concerned, mainly environmental and medical. The quartz crystal microbalance (QCM) may offer great possibilities for this purpose: a direct response signal, which characterizes the binding event between a sensitive layer, immobilized onto the surface transducer, and the analyte to be detected, can be obtained. However, for the detection of small biomolecules such as antigens, it is quite difficult to obtain an observable signal that corresponds directly to the binding event. In general, this is owing to the lack of mass sensitivity of the commonly used QCM, with 5- to 10-MHz quartz crystals. For improving this mass sensitivity, a 27-MHz quartz resonator was developed and incorporated in a flow-through microcell. Two biospecies, IgG rabbit and peroxidase enzyme, were studied with this ultra-sensitive QCM in terms of specificity, detection limit, and calibration curve.     

Electrochemical quartz crystal microbalance studies of redox polymer films

Electrochemical quartz crystal microbalance measurements are reported for redox switching of thin films of three macromolecule-metal complexes: poly(vinylferrocene) (PVF), 10% osmium-functionalized poly(vinylpyridine) (Os-PVP), and 10% osmium functionalized poly(vinylpyridine-co-styrene) (Os-PVP-co-PS). The data provide insight into the ion and solvent transfer processes associated with electron transfer between the electrode and the electroactive film. Four important parameters are identified: electrolyte composition, (co)polymer composition, prior film history and experimental time scale.     

Electrochemical quartz crystal microbalance study of ion transport accompanying charging-discharging of poly(pyrrole) films

Electrochemical quartz crystal microbalance studies on poly(pyrrole) electrodes revealed a complex nature of the potential-dependent sorption of ionic substances. It is found that the relative contribution of anions and cations to the overall charge transport process depends upon several factors, such as the oxidation state of the polymer, the composition of the supporting electrolyte as well as on the film thickness. The phenomena observed are discussed in terms of morphological transformations arising as a result of interactions between the polymer and the mobile substances. Received: 21 August 1998 / Accepted: 21 October 1998     

Electrochemical precipitation of neptunium with a micro electrochemical quartz crystal microbalance

Journal of Radioanalytical and Nuclear Chemistry - Microliter volumes are used in electrochemical detection and preconcentration of radionuclides to reduce the dose received by researchers and...     

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.     

Organic vapor detection by quartz crystal microbalance modified with mixed multilayer Langmuir-Blodgett Films

Mixed chloroform solution of Polysiloxane PS-264 and stearic acid was made into multilayer Langmuir-Blodgett (LB) films on the surface of quartz crystal microbalance (QCM). The condition for forming mixed multilayer LB films is discussed in this paper. In addition, PS-264, stearic acid and their mixture (molar ratio 1:1) were coated on the surface of QCM sensors by a spin coating method. The above modified crystals were exposed to different concentrations of various organic vapors, including related chlorinated hydrocarbons and alcohol vapors. The results of frequency changes corresponding to concentration change of the above vapors were compared. The linear regression coefficients of the QCM with LB film had better values (0.9881相似文献   

Electrochemical quartz crystal microbalance analysis of the cathodic process in a lithium-ion battery

The surface processes at carbon and platinum electrodes have been studied using the electrochemical quartz crystal microbalance technique in organic electrolyte solutions for lithium ion batteries. The changes in resonance frequency were analyzed as a function of the electrode potential, indicating that the process depended not only on the electrode material but also on the cathode potential. In the solution containing LiBF₄ as the electrolyte, the main product at the platinum surface was Li₂CO₃ and LiF, whereas formation of lithium alkylcarbonates was the primary process at the platinum and carbon electrodes in LiPF₆ solution.     

Biofouling of dextran-derivative layers investigated by quartz crystal microbalance

This study reports the fouling of carboxymethyl dextran (CMD) layers in cell culture medium, fibronectin, and serum solutions. CMD layers were covalently immobilized onto amine groups available either on an n-heptylamine plasma polymer (HApp) layer or onto a polyethylenimine (PEI) coating grafted to an acetaldehyde plasma polymer (AApp) layer. The successful immobilization of the graft layers was demonstrated by X-ray photoelectron spectroscopy (XPS). Primary amines on HApp and AApp + PEI surfaces were quantified using a colorimetric assay. Quartz crystal microbalance (QCM) was used to investigate in real-time the fouling of the graft layers upon incubation in cell culture medium (RPMI), fibronectin, and foetal bovine serum (FBS) solutions. HApp, AApp and AApp + PEI layers exhibited large fouling in fibronectin and FBS solutions, while fouling in RPMI cell culture medium was not significant. Protein repellent properties of CMD layers in FBS and fibronectin have been demonstrated compared to the other tested surfaces. QCM has shown that both CMD layers were fouled to a small extent in RPMI medium.     

电化学石英晶体微天平实时表征和定量检测短序列DNA

利用电化学石英晶体微天平(EQCM)这一灵敏的质量和电化学传感器测定特定序列DNA。应用自组装膜技术在压电石英晶振表面自组装一带羧基的α－硫辛酸单层膜,通过盐酸1-乙基-3-(3-二甲基氨基丙基)碳二亚胺(EDC)及N-羟基琥珀酰亚胺(NHS)共价固化寡聚核苷酸为探针,用于测定与其碱基序列互补的DNA。实验中EQCM实时监测了α-硫辛酸的自组装过程、探针固化过程及其与cDNA杂交过程。定量得出了探针固化量及cDNA杂交量。在酸性、中性和碱性条件下,分别对固化和杂交过程进行表征,实验发现探针固化及DNA杂交都受pH影响,本文对此现象进行了解释。同时,利用染料Hoechst33258的电化学活性,使其与双链DNA嵌合,通过测量Hoechst33258的电化学信息进一步验证了DNA杂交关键步骤。     

A quartz crystal microbalance sensor for the detection of formic acid vapors

A new quartz crystal microbalance sensor is developed to determine formic acid at low concentrations. Four previously selected polymers with acid-base characteristics were tested as possible coatings. Polyoxyethylene bis [amine] presented the best results. The sensor is rapid, sensitive [0.67 Hz/(mg/m3)], and reversible at low concentrations. The detection limit for formic acid (7.2 mg/m3) is comparable with the short term exposure limit and the threshold limit values. It presents a fast mechanical response to pressure changes, so that it can be quickly used in different environments and situations. The sensor also shows a good stability in a temperature range typical of work atmospheres (16-36 degrees C). It has a wide linear range (7.2-911.2 mg/m3) and a long useful time. It is also applicable to other low molecular mass carboxylic acids such as acetic acid.     

A quartz crystal microbalance sensor for the detection of formic acid vapors

A new quartz crystal microbalance sensor is developed to determine formic acid at low concentrations. Four previously selected polymers with acid–base characteristics were tested as possible coatings. Polyoxyethylene bis [amine] presented the best results. The sensor is rapid, sensitive [0.67 Hz/(mg/m³)], and reversible at low concentrations. The detection limit for formic acid (7.2 mg/m³) is comparable with the short term exposure limit and the threshold limit values. It presents a fast mechanical response to pressure changes, so that it can be quickly used in different environments and situations. The sensor also shows a good stability in a temperature range typical of work atmospheres (16–36 °C). It has a wide linear range (7.2–911.2 mg/m³) and a long useful time. It is also applicable to other low molecular mass carboxylic acids such as acetic acid. Received: 26 September 2000 / Revised: 8 February 2001 / Accepted: 12 February 2001     

Electrochemical quartz crystal microbalance studies of the rectified quantized charging of gold nanoparticle multilayers

Electrochemical quartz crystal microbalance (EQCM) was employed to investigate the dynamics of rectified quantized charging of gold nanoparticle multilayers by in situ monitoring of the interfacial mass changes in aqueous solutions with varied electrolytes. EQCM measurements showed that interfacial mass changes only occurred at potentials more positive than the potential of zero charge (PZC), where nanoparticle quantized charging was well-defined, whereas in the negative potential regime where only featureless voltammetric responses were observed, the QCM frequency remained virtually invariant. This was ascribed to the fact that nanoparticle quantized charging was induced by the formation of ion-pairs between hydrophobic electrolyte anions (PF6-, ClO4-, BF4-, and NO3-) and positively charged gold nanoparticles. Based on the total frequency changes and the number of electrolyte anions adsorbed onto the particle layers, the number of water molecules that were involved in the ion-pairing processes was then quantitatively estimated at varied particle charge states, which was found to increase with increasing hydrophobicity of the anions. Additionally, the electron-transfer dynamics of the gold particle multilayers were also evaluated by electrochemical impedance measurements. It was found that the particle electron-transfer rate was about an order of magnitude slower than that of the ion diffusion and binding.     

Electrochemical quartz crystal microbalance study of perchlorate and perrhenate anion adsorption on polycrystalline gold electrode

The electrochemical quartz crystal microbalance (EQCM) was used to study adsorption/desorption of perchlorate and perrhenate ions on a bare polycrystalline gold electrode. An electrode mass change in perrhenate solution was about double that of perchlorate. The equivalent mass of adsorbed anions (about 260 and 120 g F⁻¹ respectively) suggests adsorption of perchlorate and perrhenate anions on a polycrystalline gold electrode in the double-layer region. Water molecules are partially expelled from the gold surface during the initial stages of anion adsorption. The water loss is about three times larger for perrhenate compared to perchlorate due to the bigger ionic radius (volume) of the perrhenate anion.     

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。     

Study of electrochemical palladium behavior by the quartz crystal microbalance. I. Acidic Solutions

Sorption of hydrogen in a palladium electrode with a limited volume has been studied using the quartz crystal microbalance (QCM). During the hydrogen sorption process in the palladium electrode, strains are generated inside the metal which result in changes in the frequency of the crystal. These stresses change in a non-linear manner during electrode saturation, with α- and β-phases. This effect creates significant problems with the objective estimation of the amount of sorbed hydrogen inside the palladium electrode using the QCM method. This method is more accurate for the study of electrode surface processes, i.e. specific anion adsorption on the electrode surface or electrode dissolution. Received: 6 August 1998 / Accepted: 1 December 1998     

基于金纳米粒子的QCM实时检测DNA错配的研究

利用石英晶体微天平（QCM）技术,用双硫醇分子作为连接剂,将金纳米粒子固定于金电极表面,以人类p53基因片断为DNA探针,研究了其在QCM金电极表面的固定、杂交和错配,重点探讨了金纳米粒子修饰的DNA错配碱基个数和错配位点对杂交的影响。在实验条件下,金纳米粒子在QCM金电极表面的修饰使其灵敏度得到了明显提高;而且,错配碱基个数和错配碱基位点的差异都对杂交产生了不同程度的影响。     

Deliquescence phase transition measurements by quartz crystal microbalance frequency shifts

Measurements of the hygroscopic properties of aerosols are needed to better understand the role of aerosols as cloud condensation nuclei. Several techniques have been used to measure deliquescence (solid to liquid) phase transitions in particular. In this study, we have measured the deliquescence relative humidity (DRH) of organic and inorganic salts, organic acids (glutaric and succinic acid), and mixtures of organic acids with ammonium sulfate using a quartz crystal microbalance (QCM). The QCM allows for measurement of the deliquescence phase transition due to inherent measurement differences between solids and liquids in the oscillation frequency of a quartz crystal. The relative humidity dependent frequency measurements can be used to identify compounds that adsorb monolayer amounts of water or form hydrates prior to deliquescence (e.g., lithium chloride, potassium and sodium acetate). Although the amount of water uptake by a deliquescing material cannot be quantified with this technique, deliquescence measurements of mixtures of hygroscopic and nonhygroscopic components (e.g., ammonium sulfate and succinic acid (DRH > 95%)) show that the mass fraction of the deliquescing portion of the sample can be quantitatively determined from the relative change in oscillation frequency at deliquescence. The results demonstrate the use of this technique as an alternative method for phase transition measurements and as a direct measurement of the mass fraction of a sample that undergoes deliquescence. Further, deliquescence measurements by the QCM may provide improved understanding of discrepancies in atmospheric particle mass measurements between filter samples and the tapered element oscillating microbalance given the similar measurement principle employed by the QCM.     

Liposome layers characterized by quartz crystal microbalance measurements and multirelease delivery

Intact liposomes have been immobilized onto solid surfaces by a NeutrAvidin-biotin link. The construction of these layers has been followed up by X-ray photoelectron spectroscopy (XPS) and quartz crystal microbalance (QCM) measurements with energy dissipation monitoring. Also, the simultaneous release of two fluorescent probes from these liposome layers has been investigated with the aim to validate this method in multirelease delivery systems. XPS showed the successful immobilization of the different layers. XPS results also point out the importance of the deactivation method used to reveal the presence of the specific NeutrAvidin-biotin attachment. QCM measurements allowed the buildup of the different layers to be followed in real time and in situ and suggest that biotinylated liposomes stay intact upon surface attachment on NeutrAvidin-covered surfaces and had viscoelastic behavior. QCM experiments also demonstrated that surface-immobilized liposomes were able to resist irreversible adsorption from fetal bovine serum. Release kinetic profiles were studied by monitoring the release of two different fluorescent probes, namely, carboxyfluorescein and levofloxacin, from these liposome layers. These studies showed that it was possible to modulate to some extent the release rates of the two molecules by using different configurations of liposome layers.     

Electrochemical quartz crystal microbalance study of azurin adsorption onto an alkanethiol self-assembled monolayer on gold

A quartz crystal microbalance coupled with electrochemistry was used to examine the adsorption of azurin on a gold electrode modified with a self-assembled monolayer of octanethiol. Azurin adsorbed irreversibly to form a densely packed monolayer. The rate of azurin adsorption was related to the bulk concentration of azurin in solution within the concentration range studied. At a high azurin concentration (2.75 muM), adsorption was rapid with a stable adsorption maximum attained in 2-3 min. At a lower azurin solution concentration (0.35 muM), the time to reach a stable adsorption maximum was approximately 30 min. Interestingly, the maximum surface concentration attained for all solution concentrations studied by the QCM method was 25 +/- 1 pmol cm-2, close to that predicted for monolayer coverage. The dissipation was monitored during adsorption, and only small changes were detected, implying a rigid adsorption model, as needed when using the Sauerbrey equation. Cyclic voltammetric data were consistent with a one-electron, surface-confined CuII/CuI azurin process with fast electron-transfer kinetics. The electroactive surface concentration calculated using voltammetry was 7 +/- 1 pmol cm-2. The differences between the QCM and voltammetrically determined surface coverage values reflect, predominantly, the different measurement methods but imply that all surface-confined azurin is not electrochemically active on the time scale of cyclic voltammetry.     

Electrochemical deposition of poly(trans-[RuCl2(4-vinylpyridine)4]) and its reductive desorption: cyclic voltammetry and electrochemical quartz crystal microbalance studies

The electropolymerization of trans-[RuCl(2)(vpy)(4)](vpy = 4-vinylpyridine) on Au or Pt electrodes was studied by cyclic voltammetry and the electrochemical quartz crystal microbalance (EQCM) technique. Cyclic voltammetry of the monomer in DMSO on Au shows reductions at -2.0 and -2.2 V. Potential cycling over the first wave leads to polymer formation; however, scanning over the second wave leads to desorption of the polymer. These observations were confirmed by EQCM measurements which also revealed a high polymerization efficiency. Electrolysis, EQCM and XPS measurements showed that desorption was associated with substitution of chloride ligands by DMSO when the polymer was in a highly reduced state. The film also showed reversible mass changes due to the oxidation and accompanying ingress of charge-balancing anions and solvent into the film. Measurements on the dried films revealed that large quantities of solvent are trapped in the film during the electropolymerization process.