Method for measuring the losses and loading of a quartz crystal microbalance

A novel, experimentally simple, and highly sensitive method for measuring the loading of a quartz crystal resonator was developed. The method is based on the use of double-sideband suppressed-carrier modulated high-frequency signal, which is swept through the resonance range of the resonator. Induced current in the resonator is passed through a capacitor, and the voltage over the capacitor is demodulated on an analog multiplier. The phase and amplitude information is carried to the frequency-doubled modulation signal and measured on a conventional low-frequency two-phase lock-in amplifier. A complex dimensionless loading parameter is obtained from the experimental data by nonlinear model fitting. The real and complex parts of this loading parameter have a simple relationship with other parameters commonly used for characterizing the resonator loading. The performance of the method was demonstrated by measuring a series of different glycerol-water mixtures ranging from 0 up to 100% glycerol. The results were close to the shear acoustic impedance of these mixtures measured and calculated from their viscosities and densities.     

Isolated electrodeless high-frequency quartz crystal microbalance for immunosensors

This paper presents a contactless technique to measure shear bulk wave resonance frequencies of an isolated quartz crystal in a flow cell. The line antenna placed outside the cell generates and detects the resonance frequencies in a wireless-electrodeless manner. It is revealed that this mechanism relies on the quasistatic electric field. A 0.3-mm-thick AT-cut quartz was used, and its overtone resonance frequencies up to 80 MHz were measured in liquids. Exact vibrational analysis was carried out for a triple-layered resonator system consisting of the adsorbed material layer, the electrode film, and the quartz plate. It predicts higher frequency sensitivity to the adsorbed material at higher modes when the electrode layer is removed. The 13th overtone (72-MHz resonance frequency) was used to detect human immunoglobulin G with concentrations between 0.1 and 20 microg/mL captured by protein A immobilized on one side of the crystal. The real-time measurement of the frequency response yielded the equilibrium constant KA=5.21 x 10(7) M(-1).     

石英晶体元件串联谐振频率快速测量技术的研究

在介绍π网络法石英晶体元件电气参数测量原理的基础上,设计了测量系统,并对π网络输出电压以及π网络两端电压之间相位差进行分析与建模,提出迭代法和对分法相结合的快速测量算法。此结合算法测量速度快、测试精度高,适合1~200MHz频段石英晶体元件半成品加工控制和成品测量,且通过实验证明整个测量系统的测量精度和稳定性都达到国际先进水平。     

A model for the quartz crystal microbalance frequency response to wetting characteristics of corrugated surfaces

We consider the effect of surface roughness, and its unique wetting behavior, on the response of a quartz crystal microbalance (QCM) resonator operating in contact with a fluid. The rough surface is modeled as sinusoidally corrugated particular to the case of a fixed relationship between amplitude and periodicity, as would arise from polishing with monodisperse spherical particles. The penetration of fluid into the troughs of the corrugations and the resulting meniscus are determined as a competition between surface tension and compression of the trapped gas. Liquid contained below the corrugation peaks, but above the gas/liquid meniscus, is trapped and behaves as an ideal mass layer, contributing a frequency shift that adds to that arising from liquid entrainment. This model allows QCM responses on rough surfaces to be described as a function of liquid properties and contact angle. This permits responses on hydrophobic surfaces to be understood in terms of incomplete surface wetting.     

Relationships among resonant frequency changes on a coated quartz crystal microbalance, thickness changes, and resistance responses of polymer-carbon black composite chemiresistors

The relationships among frequency changes on a film-coated quartz crystal microbalance, thickness changes, and dc resistance changes have been investigated for carbon black-insulating polymer composite vapor detectors. Quartz crystal microbalance (QCM) measurements and ellipsometry measurements have been performed simultaneously on polymer films that do not contain carbon black filler to relate the QCM frequency change and the ellipsometrically determined thickness change to the analyte concentration in the vapor phase. In addition, quartz crystal microbalance measurements and dc resistance measurements on carbon black composites of these same polymers have been performed simultaneously to relate the QCM frequency change and dc electrical resistance response to the analyte concentration in the vapor phase. The data indicate that the dc resistance change is directly relatable to the thickness change of the polymers and that a variety of analytes that produce a given thickness change produce a constant resistance change for each member of the test set of polymers investigated in this work.     

Pyrene-modified quartz crystal microbalance for the detection of polynitroaromatic compounds

The synthesis of a dithiol-functionalized pyrene derivative is reported, together with studies of interactions between this receptor (and other related pyrenes) and nitroaromatic compounds (NACs), in both solution and in the solid state. Spectroscopic analysis in solution and X-ray crystallographic analysis of cocrystals of pyrene and NACs in the solid state indicate that supramolecular interactions lead to the formation of defined π-π stacked complexes. The dithiol-functionalized pyrene derivative can be used to modify the surface of a gold quartz crystal microbalance (QCM) to create a unique π-electron rich surface, which is able to interact with electron poor aromatic compounds. For example, exposure of the modified QCM surface to the nitroaromatic compound 2,4-dinitrotoluene (DNT) in solution results in a reduction in the resonant frequency of the QCM as a result of supramolecular interactions between the electron-rich pyrenyl surface layer and the electron-poor DNT molecules. These results suggest the potential use of such modified QCM surfaces for the detection of explosive NACs.     

Conventional detection of 2,4-dinitrophenol using quartz crystal microbalance

We present conventional detection of 2,4-dinitrophenol (DNP) for using the competitive reaction between DNP and DNP-conjugated albumin onto DNP antibody immobilized quartz crystal microbalance (QCM). This QCM method allows detection of DNP concentration in the range of 0.01 to 100 ng/ml; linear correlation obtains DNP concentration from 1 to 100 ng/ml.     

Piezoelectric quartz crystal microbalance sensor for trace aqueous cyanide ion determination

Using selective reaction chemistry, our present research has developed an online, real-time sensor capable of monitoring toxic cyanide at both drinking water standard and environmental regulatory concentrations. Through the use of a flow cell, aqueous samples containing cyanide are reacted with a gold electrode of a piezoelectric crystal to indirectly sense cyanide concentration by the dissolution of metallic gold. The quartz crystal is an AT-cut wafer sandwiched between two neoprene O-rings within the liquid flow cell. The presence of cyanide in solution results in the selective formation of a soluble dicyano-gold complex according to the Elsner reaction: 4Au + 8CN- + 2H2O + O2 <=> 4Au(CN)2- + 4OH-. The resulting loss of gold from the electrode is detected by the piezoelectric crystal as a resonant frequency change. Since free cyanide is a weak acid (pKa = 9.3), available protons compete for cyanide ligands. Therefore, increased sample pH provides higher sensitivity. The detection limits at pH 12 are 16.1 and 2.7 ppb for analysis times of 10 min and 1 h, respectively. The incorporation of the flow cell improves both analyte sensitivity and instrument precision, with an average signal intensity drift of only 5% over a 2-h analysis. The calibrations show excellent linearity over a variety of cyanide concentrations ranging from low ppb to hundreds of ppm. This detection method offers the advantage of selectively detecting cyanides posing a biohazard while avoiding detection of stable metal cyanides. This aspect of the system is based on competitive exchange of available metals and gold with cyanide ligands. Stable metal cyanide complexes possess a higher formation constant than cyanoaurate. This detection system has been configured into a flow injection analysis array for simple adaptation to automation. Anions commonly found in natural waters have been examined for interference effects. Additionally, the sensor is free from interference by aqueous cyanide analogues including thiocyanate. The developed detection system provides rapid cyanide determinations with little sample preparation or instrument supervision.     

Immunosensor for detection of inhibitory neurotransmitter gamma-aminobutyric acid using quartz crystal microbalance

A piezoelectric immunosensor for sensing the low molecular weight neurotransmitter gamma-aminobutyric acid (GABA), one of two major inhibitory neurotransmitters in the central nervous system, is described. The sensing interface consists of a dextran layer covalently attached to a self-assembled monolayer of thiolamine compound on the surface of gold electrodes of the crystals. The dextran layer is further modified with GABA molecules to act as the biosensing layer. The affinity binding of monoclonal anti-GABA antibody on the modified piezoelectric crystals is studied in real time without any additional labels. The equilibrium association constant, K(eq) for binding between anti-GABA antibody and GABA molecules is 14.5 microg x mL (-1). The detection limit for anti-GABA is approximately 10 nM. The sensitivity of the sensor at a concentration corresponding to half-maximal response is 13.6 ng/mL x Hz. The functionalized sensor substrate is subsequently used for competitive determination of different concentrations of free GABA (range of 5 microM-50 mM) in PBS-BSA buffer. The detection limit of the immunosensor for sensing GABA with maximum sensitivity is approximately 42 microM.     

Measurement of polystyrene photodegradation rate using a quartz crystal microbalance

Polystyrene is a very popular polymer utilised in the manufacture of various consumer products. This polymer is very cheap; however, after its usage, the slowness of its photodegradation leads to environmental pollution. In this report, the author presents a technique to systematically measure the rate of photodegradation of a thin polystyrene film. The said film was made to coat a quartz crystal microbalance (QCM) sensor. In order to detect polymer degradation and the reduction in the molecular weight, the resonance frequency of the sensor was monitored for 24 h. Results revealed that QCM sensor irradiation with ultraviolet light with a wavelength of 365 nm and optical power of 1.5 mW caused a quite significant change in the polymer structure.     

涂敷ZnO纳米线的石英晶体微天平的湿度敏感特性

采用石英晶体微天平传感器电极上旋涂纳米氧化锌薄膜,构造湿度传感敏感元件,实现对湿度检测.介绍了检测系统的组成,纳米氧化锌的制备.通过DAQ数据采集卡和Labview软件实现数据的实时采集.实验结果表明旋涂纳米氧化锌薄膜的传感器频率随测试的相对湿度变化明显,用纳米氧化锌作为敏感元件检测湿度具有很高的灵敏度和重复性.     

Nonlabeled quartz crystal microbalance biosensor for bacterial detection using carbohydrate and lectin recognitions

High percentages of harmful microbes or their secreting toxins bind to specific carbohydrate sequences on human cells at the recognition and attachment sites. A number of studies also show that lectins react with specific structures of bacteria and fungi. In this report, we take advantage of the fact that a high percentage of microorganisms have both carbohydrate and lectin binding pockets at their surface. We demonstrate here for the first time that a carbohydrate nonlabeled mass sensor in combination with lectin-bacterial O-antigen recognition can be used for detection of high molecular weight bacterial targets with remarkably high sensitivity and enhanced specificity. A functional mannose self-assembled monolayer in combination with lectin concanavalin A (Con A) was used as molecular recognition elements for the detection of Escherichia coli W1485 using a quartz crytsal microbalance (QCM) as a transducer. The multivalent binding of Con A to the E. coli surface O-antigen favors the strong adhesion of E. coli to the mannose-modified QCM surface by forming bridges between these two. As a result, the contact area between cell and QCM surface that increases leads to rigid and strong attachment. Therefore, it enhances the binding between E. coli and the mannose. Our results show a significant improvement of the sensitivity and specificity of the carbohydrate QCM biosensor with a experimental detection limit of a few hundred bacterial cells. The linear range is from 7.5 x 10(2) to 7.5 x 10(7) cells/mL, which is four decades wider than the mannose-alone QCM sensor. The change of damping resistances for E. coli adhesion experiments was no more than 1.4%, suggesting that the bacterial attachment was rigid, rather than a viscoelastic behavior. Little nonspecific binding was observed for Staphylococcus aureus and other proteins (fetal bovine serum, Erythrina cristagalli lectin). Our approach not only overcomes the challenges of applying QCM technology for bacterial detection but also increases the binding of bacteria to their carbohydrate receptor through bacterial surface binding lectins that significantly enhanced specificity and sensitivity of QCM biosensors. Combining carbohydrate and lectin recognition events with an appropriate QCM transducer can yield sensor devices highly suitable for the fast, reversible, and straightforward on-line screening and detection of bacteria in food, water, and clinical and biodefense areas.     

Photo-click immobilization on quartz crystal microbalance sensors for selective carbohydrate-protein interaction analyses

A photoclick method based on azide photoligation and Cu-catalyzed azide-alkyne cycloaddition has been evaluated for the immobilization of carbohydrates to polymeric materials. The biomolecular recognition properties of the materials have been investigated with regard to applicable polymeric substrates and selectivity of protein binding. The method was used to functionalize a range of polymeric surfaces (polystyrene, polyacrylamide, poly(ethylene glycol), poly(2-ethyl-2-oxazoline), and polypropene) with various carbohydrate structures (based on α-D-mannose, β-D-galactose, and N-acetyl-β-D-glucosamine). The functionalized surfaces were evaluated in real-time studies of protein-carbohydrate interactions using a quartz crystal microbalance flow-through system with a series of different carbohydrate-binding proteins (lectins). The method proved to be robust and versatile, resulting in a range of efficient sensors showing high and predictable protein selectivities.     

药品包衣厚度测量系统晶振频率分析及实验研究

为提高药品包衣效果和包衣质量,针对包衣厚度在线监测问题,提出基于石英晶体谐振原理的包衣厚度测量方法。利用石英晶体的压电效应原理分析石英晶体谐振片厚度剪切振动的谐振频率与包衣厚度之间的函数关系,使用等效密度法建立有限元模型并分析石英晶体谐振器在不同膜厚情况下的模态和谐振频率,理论和有限元分析结果均表明晶片的谐振频率随薄膜厚度的增加而降低,且呈近似的线性关系,检测灵敏度约为12 k Hz/μm。使用石英晶体微天平系统进行包衣厚度的测量实验,实测厚度和分析结果具有很好的一致性。研究结果表明基于石英晶体谐振的膜厚测量法可以应用于制药包衣厚度的实时测量。     

Determination of sulfur dioxide in wine using a quartz crystal microbalance

A new method for the analysis of both total and bound SO(2) in wine is proposed, based on a quartz crystal microbalance (QCM), and it is compared with the widely used Ripper method. The proposed method is faster than the Ripper's, and the instrumentation is either home-made or widely available. When both methods are applied to the same sample, the results obtained using the QCM method are bracketed in an interval less than one-tenth the size of that obtained using the Ripper method. Although the SO(2) concentrations found using the QCM method correlate well with the ones obtained with the Ripper method, the results are systematically higher, which can be explained as due to the absence of interferences known to affect the Ripper method.     

Effects of mass layer dimension on a finite quartz crystal microbalance

In this paper, a gradient crystal plasticity model in a polycrystalline grain structure is investigated. Hereby, the focus is on the influence of the grain boundary conditions. A new type of grain boundary conditions is introduced, the so-called micro-flexible boundary condition. In particular, it is compared to existing grain boundary conditions of plastic slip. Numerical results are given for the stress?Cstrain response as well as for the plastic slip field in the grain structure.     

Determination of surface-induced platelet activation by applying time-dependency dissipation factor versus frequency using quartz crystal microbalance with dissipation

Platelet adhesion and activation rates are frequently used to assess the thrombogenicity of biomaterials, which is a crucial step for the development of blood-contacting devices. Until now, electron and confocal microscopes have been used to investigate platelet activation but they failed to characterize this activation quantitatively and in real time. In order to overcome these limitations, quartz crystal microbalance with dissipation (QCM-D) was employed and an explicit time scale introduced in the dissipation versus frequency plots (Df–t) provided us with quantitative data at different stages of platelet activation. The QCM-D chips were coated with thrombogenic and non-thrombogenic model proteins to develop the methodology, further extended to investigate polymer thrombogenicity. Electron microscopy and immunofluorescence labelling were used to validate the QCM-D data and confirmed the relevance of Df–t plots to discriminate the activation rate among protein-modified surfaces. The responses showed the predominant role of surface hydrophobicity and roughness towards platelet activation and thereby towards polymer thrombogenicity. Modelling experimental data obtained with QCM-D with a Matlab code allowed us to define the rate at which mass change occurs (A/B), to obtain an A/B value for each polymer and correlate this value with polymer thrombogenicity.     

Creating gold nanoprisms directly on quartz crystal microbalance electrodes for mercury vapor sensing

A novel electrochemical route is used to form highly {111}-oriented and size-controlled Au nanoprisms directly onto the electrodes of quartz crystal microbalances (QCMs) which are subsequently used as mercury vapor sensors. The Au nanoprism loaded QCM sensors exhibited excellent response-concentration linearity with a response enhancement of up to ～ 800% over a non-modified sensor at an operating temperature of 28?°C. The increased surface area and atomic-scale features (step/defect sites) introduced during the growth of nanoprisms are thought to play a significant role in enhancing the sensing properties of the Au nanoprisms toward Hg vapor. The sensors are shown to have excellent Hg sensing capabilities in the concentration range of 0.123-1.27 ppm(v) (1.02-10.55 mg m(-3)), with a detection limit of 2.4 ppb(v) (0.02 mg m(-3)) toward Hg vapor when operating at 28?°C, and 17 ppb(v) (0.15 mg m(-3)) at 89?°C, making them potentially useful for air monitoring applications or for monitoring the efficiency of Hg emission control systems in industries such as mining and waste incineration. The developed sensors exhibited excellent reversible behavior (sensor recovery) within 1 h periods, and crucially were also observed to have high selectivity toward Hg vapor in the presence of ethanol, ammonia and humidity, and excellent long-term stability over a 33 day operating period.