基于单片机的石英晶体微天平气体检测系统设计

在对石英晶体微天平(QCM)的工作原理和检测方法进行了研究之后,本文提出采用参比QCM补偿的方法来克服温湿度等非质量因素对测量结果的影响,并研制了以MSP430F112单片机为核心的低成本的QCM气体检测系统.详细阐述了该系统的硬件结构和软件设计.为验证系统设计的合理性,用聚苯胺作为敏感材料制备了QCM氨传感器,通过并使用该系统对它性能进行检测.结果表明,与QCM传感器一起配合,该系统可以用来检测环境中气体的浓度.     

Sensing of digestive proteins in saliva with a molecularly imprinted poly(ethylene-co-vinyl alcohol) thin film coated quartz crystal microbalance sensor

The quartz crystal microbalance (QCM) has a sensitivity comparable to that of the surface plasmon resonance (SPR) transducer. Molecularly imprinted polymers (MIPs) have a much lower cost than natural antibodies, they are easier to fabricate and more stable, and they exhibit satisfactory recognition ability when integrated onto sensing transducers. Hence, MIP-based QCM sensors have been used to recognize small molecules and, recently, microorganisms, but only a few have been adopted in protein sensing. In this work, a mixed salivary protein and poly(ethylene-co-vinyl alcohol), EVAL, solution is coated onto a QCM chip and a molecularly imprinted EVAL thin film formed by thermally induced phase separation (TIPS). The optimal ethylene mole ratios of the commercially available EVALs for the imprinting of amylase, lipase and lysozyme were found to be 32, 38, and 44 mol %, respectively. Finally, the salivary protein-imprinted EVAL-based QCM sensors were used to detect amylase, lipase and lysozyme in real samples (saliva) and their effectiveness was compared with that of a commercial ARCHITECT ci 8200 chemical analysis system. The limits of detection (LOD) for those salivary proteins were as low as ～pM.     

Investigation of metallic nanoparticles adsorbed on the QCM sensor by SEM and AFM techniques

Quartz crystal microbalance (QCM) is known as a very sensitive device used for determination of mass quantity adsorbed on sensor surface. Its detection limits are in the range of ng cm\(^{-2}\). The adsorption mechanism of metallic nanoparticles on QCM sensor was investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). This study aims to highlight the importance of QCM applications in nanoparticles deposition field. The layers formed through adsorption process, induced by the oscillations of the QCM sensor, were investigated by AFM for surface topography and for particle mean size values. The morphology of layers and nanoparticles dimensions were determined by SEM. For a more complex investigation of the nanoparticles adsorption mechanism, the chemical composition of layers was achieved using SEM coupled with energy dispersive X-ray spectrometer (SEM-EDS). This preliminary research involved a new approach in characterization of metallic nanoparticles layers to achieve functional assembled monolayers.     

Small mass-change detectable quartz crystal microbalance and its application to enzymatic one-base elongation on DNA

A highly sensitive 27 MHz quartz crystal microbalance instrument with an automatic flow injection system was developed to obtain realistic minimal frequency noise (±0.05 Hz) and to obtain a stable signal baseline (±1 Hz/h) by controlling the temperature of each part in the quartz crystal microbalance (QCM) system using three Peltier devices with a resolution of ±0.001 °C and by optimizing the flow system to prevent fluctuation of the internal pressure of the QCM. The improved QCM with an automatic flow injection system enabled detection of small mass changes such as binding of biotin to a streptavidin-immobilized QCM with a high signal-to-noise ratio. We also applied this device to enzyme reactions of one-base elongation by DNA polymerase (Klenow fragment, KF). We immobilized dsDNAs including the protruding end of dA, dG, dT, or dC on the QCM electrode and ran complementary dNTP monomers with KF into the QCM flow cell. We could directly detect the enzymatic one-base elongation of DNA as a small mass increase, and we found the difference in the reaction rate for each monomer.     

A quartz crystal microbalance-based sensor system coated with functional polymers for SO2 and NO2 detection

In this work, a quartz crystal microbalance (QCM)-based adsorption sensor system with high sensitivity, selectivity, and reproducibility is designed and fabricated. The functional polymers such as polypyrrole, poly(3,4-ethylenedioxythiophene) (PEDOT), and polystyrene are coated on 8 MHz AT-cut quartz crystal surfaces as sensing materials for SO2 and NO2. All sensing materials on the QCM surface are characterized experimentally by SEM and AFM. The frequency shifts of the QCM by adsorption and desorption of gases are measured and analyzed to assess the practical applicability of the sensor system. The overall results show that the QCM coated with polypyrrole is highly selective for SO2 gas and that coated with PEDOT is for NO2. It is proven that the QCM-based adsorption sensor system is possible for monitoring SO2 and NO2 gases in the mixture of ppm level.     

Quartz crystal microbalance with integrated surface plasmon grating coupler

We have integrated a surface plasmon grating coupler into a quartz crystal microbalance (QCM) for studying surface association/dissociation reactions. In the integrated system only QCM measurement is needed to record both the optical and the acoustic signals in the same association/dissociation reaction. This integration considerably simplifies a conventional combination instrument of a grating-coupled surface plasmon resonance (SPR) spectrometer and a quartz crystal microbalance by eliminating a number of SPR components. Moreover, in the integrated system detection of the light reflections is not needed by which one bypasses the interference problem caused by two coherent light reflections off the glass window used to seal the fluid sample and off the sensor surface. The utility of the integrated system is demonstrated using a layer-by-layer polyelectrolyte multilayer deposition protocol, in which the complete features of a conventional grating-coupled SPR/QCM combination instrument are retained, including detection of optical and acoustic changes, as well as monitoring of adsorption kinetics.     

Computational studies on nitratoethylnitramine (NENA), its tautomers and charged forms

An energetic material, nitratoethylnitramine (NENA), its tautomers and also its charged forms are considered quantum chemically, using various basis sets at the levels of ab initio and density functional theories (DFT). NENA has been found to be sensitive to negative charge development, resulting in rupture of ONO(2) bond. Also conformational and molecular dynamics (MD) studies have been performed on NENA. Various geometrical parameters, energies and infrared spectra have been obtained and discussed. Also, calculations indicate that s-cis conformation of NENA is slightly more stable than the s-trans and the tautomers of it have very comparable total energy values to NENA. On the other hand, on the basis of homolytic bond dissociation energies (BDE) for ONO(2) bond in the structures, it is clear that the presence of the tautomers in the bulk of NENA somewhat should decrease its sensitivity.     

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.     

A measurement system for odor classification based on the dynamic response of QCM sensors

In this paper, an innovative measurement system for odor classification, based on quartz crystal microbalances (QCMs), is presented. The application proposed in this paper is the detection of typical wine aroma compounds in mixtures containing ethanol. In QCM sensors, the sensitive layer is, e.g., a polymeric layer deposited on a quartz surface. Chemical mixtures are sorbed in the sensitive layer, inducing a change in the polymer mass and, therefore, in the quartz resonance frequency. In this paper, the frequency shift is measured by a dedicated, fully digital front-end hardware implementing a technique that allows reducing the measurement time while maintaining a high-frequency resolution . The developed system allows, therefore, measuring variations of the QCM resonance frequency shifts during chemical transients obtained with abrupt changes in odor concentration. Hence, the reaction kinetics can be exploited to enhance the sensor selectivity. In this paper, some measurements obtained with an array of four sensors with different polymeric sensitive layers are presented. An exponential fitting of the transient responses is used for feature extraction. Finally, to reduce data dimensionality, principal component analysis is used.     

Acoustic and Optical VOCs Sensors Incorporating Carbon Nanotubes

The authors investigate the sensing properties of single-walled carbon nanotubes (SWCNTs) films, which are used as nanostructured materials for chemical sensors onto three types of transducers using different principles of operation as surface acoustic waves (SAWs), quartz-crystal microbalance (QCM), and a standard silica optical fiber (SOF) for detection of volatile organic compounds at a room temperature. The sensing probes have been configured as 315- and 433-MHz SAW two-port resonator-based oscillator, 10-MHz QCM resonator, and SOF light-reflectometry-based system at a wavelength of 1310 nm. A nanocomposite film of SWCNTs embedded in a cadmium-arachidate matrix was deposited by Langmuir-Blodgett (LB) technique onto the SAW sensors. An LB multilayer of SWCNTs-onto-CdA buffer material was also deposited onto the QCM and SOF sensors. The experiments demonstrate that carbon-nanotubes acoustic and optical sensors are highly sensitive to a wide range of polar and nonpolar organic solvents up to a sub-ppm detection limit at a room temperature.     

A novel technique to immobilize DNA on surface of a quartz crystal microbalance by plasma treatment and graft polymerization

A quartz crystal microbalance (QCM) is well known to provide mass-sensitive devices in nanogram levels, because of the resonance frequency changes upon the adsorption on the electrode. It offers the possibility of monitoring hybridization in real time and with high selectivity. In this study, a biosensor system was developed for the detection of Vibrio parahaemolyticus via its oligonucleotide probe immobilized on the gold electrodes' surface of QCM. However, because the surface of QCM was an inorganic substance, it was difficult to immobilize the oligonucleotide probe. In this study, the plasma surface modification of QCM through deposition of hexamethyldisilazane (HMDSZ) films as an interlayer was investigated. The interlayer provided good adhesion to the substrate and had a uniform structure. The result indicates that plasma deposition was a useful technique to immobilize the oligonucleotide probe on the gold electrodes' surface via glutaraldehyde (GA) coupling. To improve immobilization, post treatments by surface grafting of acrylamide (AAm) and polyethyleneimine (PEI) treatment onto the electrodes were also performed. The result demonstrates that the shift of resonance frequency of QCM was improved via subsequent graft polymerization of AAm and PEI treatment onto the electrodes. The QCM sensor after plasma deposition and surface modification could provide detection sensitivity up to 86 ng/ml and kept at 88% detecting sensitivity after 19 days of storage at 0 °C. After washing with 0.1 M NaOH solution and 7 times of repeated use in detecting, the regeneration rate of QCM could be up to 60%.     

Effect of polyelectrolyte multilayers on the response of a quartz crystal microbalance

The effect of a polyelectrolyte (PE) multilayers made by a layer-by-layer technique on the response of a quartz crystal microbalance (QCM) is studied by using novel mathematical methods based on the M?bius transformations and their matrix representations in the complex plane. In the first method, the basic properties of the M?bius transformation are used for obtaining the PE bilayer matrix from the QCM impedance measurements taken at four different numbers of layers. In the second method, nonlinear fitting with concomitant error estimation is used for obtaining the elements of the bilayer matrix. The methods are applied to a multilayer composed of 150 bilayers of poly(sodium 4-styrenesulfonate) and poly(diallyldimethylammonium) chloride on a quartz crystal resonator. The structure of the system is discussed, and the bulk acoustic impedance and areal mass density of the bilayer are calculated from the layer matrix.     

Transition liquid phase bonding of a Hastelloy X and the bond strength at 1173 K

Transition liquid phase (TLP) bonding has been conducted on a Hastelloy X using amorphous foil filler metals. The inserted fillers were made by rapid solidification of a Ni-15% Cr alloy containing 3 to 5 mass% boron as a melting point depressant. The microstructural change with isothermal bonding time from 2.4 to 38.4 ks was examined in the bond regions by optical microscopy and electron probe microanalysis (EPMA). An assessment of the bond strength was made by stress rupture tests performed at 1173 K. It was found that rupture strain and rupture life increased with increasing bonding time. A bond efficiency greater than 80% was achieved when the bonding time was 38.4 ks.     

QCM Operation in Liquids: An Explanation of Measured Variations in Frequency and Q Factor with Liquid Conductivity

Recently, several reports have shown that when one side of a quartz crystal microbalance (QCM) is exposed to a liquid, the parallel (but not the series) resonant frequency is influenced by the conductivity and dielectric constant of the liquid. The effect is still controversial and constitutes a serious complication in many applications of the QCM in liquid environments. One suggestion has been that acoustically induced surface charges couple to charged species in the conducting liquid. To explore this effect, we have measured the parallel and the series mode resonance frequencies, and the corresponding Q factors, for a QCM with one side facing a liquid. These four quantities have all been measured versus liquid conductivity, using a recently developed experimental setup. It allows the simultaneous measurement of the resonant frequency and the Q factor of an oscillating quartz crystal, intermittently disconnected from the driving circuit. Based on these results, a simple model together with an equivalent circuit for a quartz crystal exposed to a liquid is presented. The analysis shows that it is not necessary to infer the existence of surface charges (or other microscopic phenomena such as electrical double layers) to account for the influence of the liquid's electrical properties on the resonant frequency. Our results show that the contacting conductive liquid, in effect, enlarges the electrode area on the liquid side and thereby changes the parallel resonant frequency. By proper design of the QCM measurement, perturbing effects due to the liquid's electrical properties can be circumvented.     

Layer-by-layer of liposomes and membrane protein as a recognition element of biosensor

Layer-by-layer (LBL) assembly composed of liposome and membrane protein, bacteriorhodopsin (bR) was fabricated on quartz crystal microbalance (QCM) as a sensor element for bio-recognition. The LBL assembly was prepared by stacking of liposome/bR solutions alternately with a flowing system. By atomic force microscopy (AFM) and the QCM monitoring the bR and the liposome were found to be stacked regularly until the 8th layer of the liposome. The fabricated LBL assembly on the QCM was engaged to detect nonylphenol in solution, which is one of the endocrine disrupting chemicals. It was confirmed that the existence of nonylphenol in solution can be detected by a mass decrease of the LBL assembly on the QCM, which is caused by the disruption of the liposome through nonylphenol, in the low concentration range of 0.1–10 ppm.     

Detection of point mutation and insertion mutations in DNA using a quartz crystal microbalance and MutS, a mismatch binding protein

MutS protein is a mismatch binding protein that recognizes mispaired and unpaired base(s) in DNA. In this study, we incorporate the MutS protein-based mutation recognition into quartz crystal microbalance (QCM) measurements for DNA single-base substitution mutation and 1-4 base(s) insertion (or deletion) mutation detection. The method involves the immobilization of single-stranded probe DNA on a QCM surface, the hybridization of target DNA to form homoduplex or heteroduplex DNA, and finally the application of MutS protein for the mutation recognition. By measuring the MutS binding signal, DNA containing a T:G mismatch or unpaired base(s) is(are) discriminated against perfectly matched DNA at target concentrations ranging from 1nM to 5 microM. Furthermore, the QCM damping behavior upon MutS-DNA complex formation is studied using a Network Analyzer. The measured motional resistance changes per coupled MutS unit mass (deltaR/deltaf) are found to be indicative of the viscoelastic or structural properties of the bound protein, corresponding to different binding mechanisms. In addition, the deltaR/deltaf values vary remarkably when the MutS protein binds at different distances away from the QCM surface. Thus, these values can be used as a "fingerprint" for MutS mismatch recognition and also used to quantitatively locate the mutation site.     

Quartz crystal microbalance study of DNA immobilization and hybridization for nucleic Acid sensor development

The immobilization of two 30-mer oligonucleotides, one biotinylated (biotin-DNA) and the other having a mercaptohexyl group at the 5'-phosphate end (BS1-SH), onto modified gold surfaces has been examined using a quartz crystal microbalance (QCM). Both single-layer and multilayer DNA films were prepared. The single-layer films of biotin-DNA were constructed by binding to a precursor layer of avidin, which had been attached to the QCM either covalently using a water-soluble carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) or via electrostatic interaction with poly(allylamine hydrochloride) (PAH). Single-layer films of BS1-SH were also formed on PAH via the electrostatic attraction between the amine groups on PAH and the negatively charged phosphate backbone of DNA. Multilayer films of DNA were fabricated by the successive deposition of avidin and poly(styrenesulfonate) (PSS), up to a total of nine avidin/PSS layers, followed by DNA adsorption. DNA immobilization and hybridization of the immobilized DNAs was monitored in situ from QCM frequency changes. Hybridization was induced by exposure of the DNA-containing films to complementary DNA in solution. Equal frequency changes were observed for the DNA immobilization and hybridization steps for the single-layer films, indicating a DNA probe-to-hybridized DNA target ratio of 1:1. The multilayer DNA films also exhibited DNA hybridization, with a greater quantity of DNA hybridized compared with the single-layer films. The multilayer films provide a novel means for the fabrication of DNA-based thin films with increased capacity for nucleic acid detection.     

The influence of corrosion on bond properties between concrete and reinforcement in concrete structures

The rebar corrosion in reinforced concrete is one of the most extensive pathologies affecting the performance of concrete structures. Chloride-induced rebar corrosion damage results mainly from the use of de-icing salts in cold climates and/or exposure to marine environments. Carbonation damage is a further important degradation mechanism. The internal consequences of corrosion are the modification of the steel behavior and degradation of the steel–concrete bond. This work is devoted to the influence of the controlled corrosion on the adherence between steel and concrete. A new geometry of specimen has been designed to: (i) avoid the lateral confining stresses that appear during the classical pullout tests and (ii) permit to impose a known confinement for the study of its influence on the behavior of the interface. Five specimens with different levels of corrosion have been tested in this contribution. Reinforcing bars embedded in concrete were submitted to accelerated corrosion using an external current source. The magnitude of corrosion was measured using both Faraday’s law and the weight loss method. The level of corrosion varied from 0% to 0.76%. The geometry of the specimens allowed us to take series of digital pictures during the tests, which were analyzed using a digital image correlation, the procedure named CORRELI^LMT. The results of pullout tests proposed in this contribution indicate that: (i) levels of corrosion that are less than 0.4% of weight loss improves the bond stress and (ii) levels of corrosion resulting in more than 0.4% of weight loss lead to a reduction of the bond stress value.     

Simple low-vacuum coating of paraffin wax on carbonaceous gas sensing layers

A simple low-vacuum coater has been fabricated by using a vacuum resin degassing chamber, in which an aluminum effusion cell is heated by a soldering iron. Our developed vacuum coater presents the versatile methods for depositing paraffin wax for skin-coating the sensing layers of quartz crystal microbalance (QCM). As the increase of the cell temperature, the thickness and inhomogeneity of the wax films were increased. Impedance analyses revealed that the energy dissipation of the QCM was remarkably enhanced with the amount of wax. It was also revealed that the as-deposited wax was fluidic until coagulation by heat radiation. This surface skin coating enhanced the ethyl acetate (EA) sorption capabilities of the polyethylene-sputtered QCM sensor, whereas, it reduced the EA sorption capacity of the d-phenylalanine-sputtered QCM sensor.     

Characterization of surface modification on self-assembled monolayer-based piezoelectric crystal immunosensor for the quantification of serum α-fetoprotein

Self-assembled monolayers (SAMs) on coinage metallic material can provide versatile modeling systems for studies of interfacial electron transfer, biological interactions, molecular recognition and other interfacial phenomena. Recently, a bio-sensing system has been produced by analysis of the attachment of antibody using alkanethiols, to form SAMs on the face of Au-quartz crystal microbalance (QCM) surfaces. In this study, the attachment of anti-α-fetoprotein monoclonal antibody to a SAMs surface of 11-mercaptoundecanoic acid was achieved using water-soluble N-ethyl-N′-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide as coupling agents. Surface analyses were utilized by X-ray photoelectron spectroscopy and atomic force microscopy. The quantization of immobilized antibody was characterized by the frequency shift of QCM and the radioactivity change of ¹²⁵I labeled antibody. The limit of detection and linear range of the calibration curve of the QCM method were 15 ng/ml and 15–850 ng/ml. The correlation coefficients of α-fetoprotein concentration between QCM and radioimmunoassay were 0.9903 and 0.9750 for the standards and serum samples, respectively. This report illustrates an investigation of SAMs for the preparation of covalently immobilized antibody biosensors.