Improvement of latex piezoelectric immunoassay: Detection of rheumatoid factor

Latex piezoelectric immunoassay is a method for detection of agglutination of antibody- or antigen-bearing latex by immunoreaction using a piezoelectric quartz crystal; the agglutination decreases the oscillation frequency of the crystal. This is advantageous in that coating the surface of the crystal followed by fixation of antibody or antigen is unnecessary. There is, however, a drawback, and to improve this, we designed a micro-cell in which only one side of the crystal is exposed to the solution. A method for regenerating the crystal was also devised. Measurement was carried out using a calibration curve of the frequency change against rheumatoid factor activity. The improvement made it possible to use one crystal repeatedly and reproducibility was satisfactory. The calibration curve became almost independent of the crystal used.     

Latex piezoelectric immunoassay: Effect of interfacial properties

Latex piezoelectric immunoassay is a technique for detecting agglutination of antibody- or antigen-bearing latex by an immunoreaction using a piezoelectric quartz crystal; the agglutination decreases the oscillation frequency of the crystal. This is advantageous in that immobilization of antibody or antigen on the crystal surface is unnecessary. In this report, different kinds of chemical functional groups were immobilized on the electrode surface, allowing us to consider the effect of interfacial structure on the frequency change. Electrode modifications such as self-assembly of alkanethiol and aminoalkoxysilane monolayers, and polyethylenimine-glutaraldehyde coating as well as plasma treatment were examined. The sensitivity of the system was found to imitate the interfacial properties so that modification of the electrode surface could improve the response. Among the methods examined for this electrode surface modification, the polyethylenimine-glutaraldehyde modification had the advantages of high reproducibility, fast operation and simplicity. It was also suggested that the frequency change originated primarily from the immunoreaction at the interface.     

A novel piezoelectric immunosensor for detection of carcinoembryonic antigen

A simple, rapid, and highly sensitive immunosensor for the direct determination of carcinoembryonic antigen (CEA) in human serum using a piezoelectric crystal has been developed and optimized. In order to improve sensitivity of the immunosensor, a protein A-based orientation-controlled immobilization method for antibodies was adopted together with an immunoreactive accelerant of polyethyleneglycol (PEG) used to amplify the signal response of frequency. Human normal serum was utilized as a reference background. The linear range for CEA concentration obtained by the end-point method was 66.7-466.7 ng/mL. Clinical samples from cancer patients were analyzed by the proposed piezoelectric immunoassay, and the analytical results were reasonably comparable with those obtained by the chemiluminescence immunoassay (CLIA). The proposed immunosensor provides a new promising method for the highly sensitive immunoassay of CEA in clinical laboratory.     

Monitoring iodine adsorption onto zeolitic-imidazolate framework-8 film using a separated-electrode piezoelectric sensor

In this work, a separated-electrode piezoelectric sensor (SEPS), constructed by a naked quartz crystal mounted between two electrodes, is reported for applications in a corrosive gaseous phase. The response of SEPS was measured by an impedance analysis method. It was shown that SEPS has an excellent frequency stability because its quality factor is in the order of 10⁵. The SEPS can be operated even with the electrode gap in air larger than 1 cm. Compared with a conventional quartz crystal microbalance, the resonant frequency of the SEPS is independent of the mass change in the electrode. The SEPS was applied to monitor the adsorption of iodine on quartz surface and zeolitic-imidazolate framework-8 (ZIF-8) film as well as in the transfer of iodine between two ZIF-8 films. The SEPS offers the advantages of easy preparation, corrosion-resistant and convenience in combination with mass and optical measurements.     

Adsorption of metal ions from solution onto a piezoelectric quartz crystal

Many metal ions are spontaneously adsorbed onto a piezoelectric quartz crystal and change the oscillation frequency. The pH ranges in which the metal ions adsorbed were just below that of precipitate formation as the ‘hydroxides’; frequency changes caused by adsorption were not observed in these pH ranges where the ‘hydroxides’ formed. Cationic organic reagents, such as crystal violet and methylene blue, were also adsorbed on the piezoelectric quartz crystal but non-ionic and anionic organic compounds were not. These results showed that the crystal was negatively charged on the surface.     

Electrochemically modified piezoelectric crystal biosensor for detection of Staphylococcus aureus

Electropolymerized o-phenylenediamine film is used as a functional coating for the immobilization of anti-S. aureus antibody on the surface of a gold-plated piezoelectric crystal, and this piezoelectric immunosensor is applied to detect S. aureus. The frequency shift (F = F20s - F380s, Hz) between the frequency at the 20th second (after the addition of sample, F20s) and that at 380 seconds later (F380s) was introduced to construct a calibration graph, and shortening of assay time was achieved. The S. aureus concentrations in the range of 105-109 cells/mL can be detected by this system.     

Detection of odorants using lipid-coated piezoelectric crystal resonators

Lipid-coated piezoelectric crystal resonators were applied to the detection of odorants. An impedance analyser and microcomputer were used for resonant frequency measurements. Asolectin, cholesterol, lecitin (from egg) and phosphatidylethanolamine were used as the coating film, and amylacetate, critical, β-ionane, menthone and other organic gases were detected. The miniumum concentration of a variety of odorants required to change the resonant frequency corresponded to the results previously reported from olfactory cells. After normalization of resonant frequency response values for amount of coating, the resonator could be used to detect odorants at levels down to ca. 1μl l^-1.     

Preparation and application of cryptand-coated piezoelectric crystal gas-chromatographic detector

A re-usable and sensitive cryptand-22-coated quartz-crystal membrane piezoelectric sensor with a homemade computer interface for signal acquisition and data processing was prepared and applied as a gas-chromatographic (GC) detector for various organic molecules. The oscillating frequency of the quartz crystal decreased due to the adsorption of organic molecules on cryptand-22. Effects of functional group, molar mass, steric hindrance and polarity of organic molecules on frequency responses of the cryptand-coated piezoelectric crystal detector were investigated. The cryptand-coated piezoelectric crystal GC detector had demonstrated high sensitivity for various polar organic molecules and good reproducibility when re-used. The frequency responses of the cryptand-coated crystal for various molecules were in the following order: carboxylic acids (RCOOH)primary amines (R-NH₂)>alcohols (ROH)>secondary amines (R₂NH)>tertiary amines (R₃N)>ketones. More polar molecules exhibited better frequency responses. The effect of temperature and amount of coating on the frequency responses of cryptand-coated crystal GC detector were also investigated. The cryptand-coated piezoelectric crystal GC detector compared well with the commercial thermal conductivity detector (TCD).     

Electrodeless piezoelectric quartz crystal and its behaviour in solutions

An electrodeless piezoelectric quartz crystal system was constructed with a quartz crystal plate, electrolyte solutions and platinum plates or rods immersed in the solutions for connecting to an oscillator, instead of the electrodes. The crystal without electrodes oscillates in the solutions. The frequency varies with temperature, specific conductance of the solutions and the mass change of the plate caused by the adsorption of material from the solution in, the same way as a normal piezoelectric quartz crystal with electrodes.     

Determination of phenytoin by modified extraction-gravimetry with a piezoelectric transducer

An extraction-frequencymetric method has been proposed for the determination of phenytoin sodium using a newly developed ring-coated piezoelectric crystal transducer. The sample solution is acidified with HCl and the liberated free phenytoin is extracted with 1,2-dichloroethane. The extract is applied to a ring-coated quartz crystal in nitrogen stream and after 2 min the crystal frequency is measured. The frequency change due to the deposited phenytoin is proportional to the phenytoin sodium content in the range 0.02–1.2 g. The method can be applied to the assay of phenytoin sodium tablets and injections.     

Determination of bioelectrochemical parameters of red cell using a piezoelectric crystal sensor

Based on the impedance behavior of red cell at high frequency, the frequency response of series piezoelectric crystal sensor in the red cell suspension was derived and verified experimentally. A method of using piezoelectric crystal sensor to determine the conductivity of the interior of the cell was proposed. The experimental results show that the mean conductivity of rabbit red cell cytoplasm was 0.269 S/m and the mean shape factor of red cell was 2.05.     

Microdetermination of sulfite with a piezoelectric crystal detector

A piezoelectric method is proposed for the determination of sulfite in concentration range 1 × 10^–7–1 × 10^–5 mol/1. The method is based on the redox reaction of sulfite with iodine followed by measuring frequency change of the piezoelectric crystal caused by the unreacted iodine. The method is applied to the determination of sulfite in liquor.     

Comparison of two methods for coating piezoelectric crystals

Quartz piezoelectric crystals were coated with triethanolamine using two procedures: spray and syringe methods. The reproducibility of both coating methods was evaluated comparing the relative standard deviation of batches of four crystals coated by each of the procedures. The relative standard deviation obtained with the spray method is a hyperbolic function of the coating frequency and is, at least, three times lower than the one calculated from results of the syringe method, which is not frequency dependent. An explanation for the poorer reproducibility of the syringe method is given, based on the radial sensitivity theory and the non-uniformity of the coating distribution over the crystal, as evidenced by microscopic photographs.     

Detection of lipopolysaccharide binding peptides by the use of a lipopolysaccharide-coated piezoelectric crystal biosensor

A method has been developed to monitor the interaction between a lipopolysaccharide (LPS) and LPS-binding peptides using a piezoelectric quartz crystal (PQC). Different pH conditions were evaluated to coat LPS onto AT-cut crystals that had been sputtered with gold and carboxylated with a 4,4-dithiodi(n-butyric acid). The optimal pH for LPS coating onto the crystal was 4–5. Synthetic peptides that represent different regions of human bactericidal/permeability-increasing protein, BPI (BPI 85–99, BPI 90–101, BPI 157–167) and polymyxin B (PmB) as well as negative control peptide (HBsAg 139–147) were utilized to compare their binding ability to this LPS-coated PQC sensor. The results showed that PmB gave the greatest decrease to the resonant frequency indicating greatest binding ability. BPI 85–299, considered the main part of the LPS binding domain of BPI, was the next greatest, while BPI 157–167 and HBsAg 139–147 showed little response. In addition, BPI 90–101 and PmB-mimicking peptide showed intermediate LPS-binding ability, which was less than that of BPI 85–99, but was higher than that of BPI 157–167. These results suggest the PQC biosensor is potentially useful for the detection and comparison of the LPS-binding ability of different peptides by using an LPS-coated piezoelectric crystal.     

Monitoring of mutagenic process with piezoelectric quartz crystal impedance analysis

A novel method for monitoring of mutagenic process of dimethyl sulfate to Salmonella typhimurium strain (TA100) was proposed by using piezoelectric quartz crystal impedance (PQCI) analysis technique. The time courses of responses piezoelectric impedance parameters for a quartz crystal in a culture system were simultaneously obtained and discussed. It was found that the motional resistance variation (DeltaR(m)) increases and frequency shift (Deltaf) of PQC sensor decreases correspondingly during the mutagenic process of the bacteria. These parameters could reflect the variations of viscosity and density of culture system. By fitting DeltaR(m) versus time curves toward Gompertz bacterial growth model, we obtained and discussed the bacterial growth parameters for both normal growth and mutagenic process. The experiments showed that the proposed method could provide real time and multidimensional impedance information to the monitoring of mutagenic process.     

压电晶体传感器阵列在补体系统免疫分析中的应用

将压电石英晶体阵列应用于补体系统免疫分析中,从而发展了一种新型的同步免疫分析方法,并对补体系统的四种成分（C4,C5,C1q,B因子）进行了分析测试。通过对不同条件（即抗体效价不同）下的多组分分析物进行同步检测,研究了补体系统免疫反应的特性和该传感器阵列的响应特性。差频信号的测量消除了粘度、温度和电导率的影响,同时对该传感器阵列晶体间的干扰进行了测试。该方法操作简单、准确、灵敏度较高。     

Construction and analytical application of ion-selective piezoelectric sensor for atropine sulfate

The method describes the use of a piezoelectric quartz crystal (PQC) as a substitute for ion-selective electrodes. The approach is feasible when the membrane materials are electrically non-conductive and membrane potential measurements are consequently not possible. An ion-selective piezoelectric sensor sensitive to atropine sulfate was constructed by coating a PVC membrane containing activant on one the side of a PQC. On the basis of selective adsorption of atropine ions across the modified film and the sensitive mass response of PQC, the method exhibits a sensitive, rapid response and is easy to operate without pretreatment of the sample. The logarithm of the frequency shift gave a linear relationship with the logarithm of atropine sulfate concentration in the 1.0 x 10(-8)-1.0 x 10(-3) M range with a detection limit of 5.0 x 10(-9) M at pH 7.0. Recoveries were from 98.7-102.2%. Two activants, atropine tetraphenylborate and atropine dipicrylaminate, were synthesized and investigated. Influencing factors were also examined and optimized. The results for real samples obtained by the proposed method agreed with those obtained by conventional methods.     

Electrochemical piezoelectric quartz crystal impedance study on the interaction between concanavalin A and glycogen at Au electrodes

The carbohydrate research has emerged as a "new frontier" in chemical/biological field. The binding of lectin with carbohydrate is one of the important courses of life activities. The report studies concanavalin A (Con A)-glycogen interaction on gold electrode surfaces by electrochemical piezoelectric quartz crystal impedance (EPQCI) method. The piezoelectric quartz crystal (PQC) parameters, resonant frequency shift (Deltaf(0)) and the motional resistance change (DeltaR(1)), and the electrochemical impedance (EI) parameters, electrolyte resistance change (DeltaR(s)) and the double layer capacitance change (DeltaC(s)), were measured and discussed simultaneously. Two methods were adopted for measuring the Con A-glycogen association. Based on EPQCI measurement during Con A reaction with glycogen adsorbed on Au electrode, association constant K(a) and the amount of the binding sites s calculated are 1.48 x 10(6) M(-1) and 4.09, respectively. Based on single PQC measurement of glycogen reaction with Con A assembled on Au electrode, K(a) was estimated to be 1.26 x 10(6) M(-1).     

A conductance sensor for dissolved sulphur dioxide using a series piezoelectric crystal device

A new piezoelectric crystal impedance sensor for the determination of sulphur dioxide in aqueous solution is presented. It is realized using a series piezoelectric crystal device which is constructed by connecting an AT-cut piezoelectric crystal to a probe in series. The probe is filled with an internal electrolyte solution that is separated from sample solutions by a gas-permeable membrane. The present sensor exhibits a favourable frequency response to 1 x 10(-7)-1 x 10(-3) M sulphur dioxide. The detection limit is 1 x 10(-8) M. The effects of the sensor preparation are considered. Dynamic range, reproducibility, response time and selectivity of the sensor are also discussed. The proposed sensor has been used successfully for lamp sulphur determinations in petroleum samples.     

Adsorption studies of dodecylamine at the quartz interface using an electrode-separated piezoelectric sensor

The adsorption process of dodecylammonium chloride (DAC) from aqueous solutions onto a quartz crystal interface was investigated in situ using an electrode-separated piezoelectric sensor (ESPS). Increasing amounts of DAC adsorbed onto a quartz crystal surface resulted in linearly decreasing oscillating frequencies of the ESPS. The adsorption density can be monitored by the frequency decrease. The adsorption density obtained by calculation using the Sauerbrey equation in the ESPS method is greater than that in solution depletion method. A calibration coefficient is added into the Sauerbrey equation to correct the influence of surface roughness of the quartz crystal on the adsorption density. The influence of solution properties on the adsorption density measurement was discussed. A dependence of the adsorption density on pH was reported. Received: 17 April 1997 / Revised: 1 December 1997 / Accepted: 7 December 1997