THEORY AND APPLICATIONS OF FREQUENCYMETRIC TITRATION

Theory on frequencymetric titration has been proposed based on equivalent circuit of piezoelectric quartz crystal (PQC) in liquid and oscillation equation of TTL-PQC oscillator, and the theoretical equation derived representing the frequency shift with respect to the solution conductivity. Practical examples of various types of titration are given in this paper.     

In Situ Monitoring of Generation and Precipitation of Ferric Hydroxide Sol with a Piezoelectric Quartz Crystal Impedance Analyzer

The piezoelectric quartz crystal (PQC) impedance technique was applied to monitor in situ generation and precipitation of the ferric hydroxide sol in aqueous solutions at 90 degrees C. Equivalent circuit parameters and resonant frequencies as well as the half-peak width of the electroacoustic conductance spectrum deltaf(G1/2) for the PQC resonance were obtained and analyzed. Three stages, sol generation and simultaneous adsorption, adsorption equilibrium, and precipitation of ferric hydroxide sol could be identified in the process of adding the ferric nitrate solution into the hot water. A scheme of two consecutive reactions occurring at the electrode/solution interface was used to analyze the adsorption kinetics of ferric hydroxide sol onto the Au electrode. In addition, the electrolyte-induced precipitation of the colloid was monitored and discussed. Temperature effect on the PQC resonance behavior in liquid was also investigated. Since the PQC impedance technique provides multidimensional piezoelectric information in situ, it is highly recommended for studying the process of sol-gel generation and precipitation. Copyright 2001 Academic Press.     

溶菌酶在裸金电极和疏基乙酸或正十二疏烷基醇修饰电极上的吸附

电化学石英晶体阻抗系统;疏基乙酸;溶菌酶在裸金电极和疏基乙酸或正十二疏烷基醇修饰电极上的吸附     

Adsorption behavior of metal ions onto a bovine serum albumin (BSA) membrane monitored by means of an electrode-separated piezoelectric quartz crystal.

The interaction between metal ions and bovine serum albumin (BSA) was studied by using a piezoelectric quartz crystal (PQC) arranged in the electrode-separated configuration. A silanized surface of the PQC was coated with a BSA membrane via a coupling reaction with glutaraldehyde. The frequency shifts obtained from PQC coated with a BSA membrane suggested that various kinds of metal ions could be adsorbed onto the BSA membrane from aqueous solutions containing a low concentration of metal ions (2 or 10 micromol dm(-3)), only when the BSA was denatured with an alkaline solution. Anionic species of Pt(IV) and Au(III) were adsorbed onto the denatured BSA membrane from an acetic acid solution at pH 2.2, and cationic species of Cd(II), Zn(II), Co(II), Ni(II), Cu(II), and Ag(I), and cations, such as Ca2+, Ba2+, and Mg2+, were adsorbed from ammonia buffer at pH 9.5, whereas Al(III), Cr(III), Fe(III), Hg(II), and Pb(II) were hardly adsorbed. The adsorption mechanisms of these metal ions are discussed, based on the electrostatic interaction between the metal ions and the denatured BSA membrane, and complex formation between the metal ions and amino acid residues of the denatured BSA. Further, the PQC coated with a denatured BSA membrane was applied to the determination of Pt and Cd, using large frequency shifts for Pt(IV) and Cd(II).     

A comparative study on the viscoelasticity and morphology of polyaniline films galvanostatically grown on bare and 4-aminothiophenol-modified gold electrodes using an electrochemical quartz crystal impedance system and SEM.

The equivalent-circuit parameters of the 9-MHz piezoelectric quartz crystal (PQC) resonance were measured in situ during the galvanostatic polymerization of aniline on 4-aminothiophenol(4-ATP)-modified and bare Au electrodes for ca. 2000 s, respectively. Two polymerization media, 0.100 mol L-1 aniline in 1.0 mol L-1 H2SO4 and in 2.0 mol L-1 HClO4 aqueous solutions, and two values of the current density, 12 and 36 microA cm-2, were used. At identical levels of the resonant frequency shifts in the solutions, obviously greater increases in the motional resistance (R1) were found after aniline polymerization on bare Au electrodes, though the absolute values of delta f0/delta R1 were all large; also, the resonant frequency shifts in air (delta f0g) were considerably smaller for PANI films grown on bare Au electrodes. It is thus concluded that, under identical polymerization conditions, (1) the PANI film grown on a bare gold electrode is rougher, less compact, and can entrap solution more notably; (2) the deposition efficiency of PANI is higher on a 4-ATP-modified Au electrode, owing to a significantly greater observed "dry" frequency shift, and thus a greater "net" mass value of the polyaniline backbone. SEM observations have confirmed that PANI films on 4-ATP-modified Au electrodes were smoother and more compact than those grown on bare Au ones under identical polymerization conditions. In addition, a technique of simultaneous measurements of the electroacoustic admittance of the PQC resonance and the electrochemical impedance was used to monitor the adsorption of 4-ATP onto a PQC gold electrode.     

A novel dual-impedance-analysis EQCM system--investigation of bovine serum albumin adsorption on gold and platinum electrode surfaces

Both quartz crystal micro-balance (QCM) impedance and electrochemical impedance spectroscopy (EIS) methods are widely used in interface studies. This paper presents details about a new strategy for simultaneous, mutual-interference-free and accurate measurements of QCM impedance and EI, through connecting a suitable capacitance in series with the piezoelectric quartz crystal (PQC) between QCM impedance and EIS measurement instruments. Combined and individual measurements of QCM impedance and EIS during silver deposition gave results comparable with each other, demonstrating the reliability of the proposed method. Bovine serum albumin (BSA) adsorption on gold and platinum electrodes in Britton-Robinson (B-R) buffers was investigated, and the Fe(CN)6(3-)/Fe(CN)6(4-) couple was used as an electrochemical probe to characterize BSA adsorption. While the reversibility of Fe(CN)6(3-)/Fe(CN)6(4-) couple on bare Au and Pt electrodes changed very slightly with decreasing solution pH from pH approximately 7 to pH approximately 2, the standard rate constant (ks) of this couple increased abruptly with solution pH below pH approximately 4.5 at a BSA-modified Au electrode, but decreased with solution pH at a BSA-modified Pt electrode. By analyzing the QCM impedance data with a modified BVD equivalent circuit and the EI data with a modified Randle's equivalent circuit, inflexion changes at pH approximately 4.5 were all found at pH-dependent responses of the resonant frequency, the double-layer capacitance, the capacitance of the adsorbed BSA layer, the peak-absorbance values of BSA solutions at 277.5 and 224.5 nm, and so on. It was also found that a BSA adsorption layer can effectively inhibit gold corrosion during ferrocyanide oxidation in a ferrocyanide-containing BR solution. Some preliminary explanations of these findings have been given. The proposed method is highly recommended for wider applications in surface science.     

A new study of the degradation of hyaluronic acid by hyaluronidase using quartz crystal impedance technique

A new quartz crystal impedance sensing technique for the assay of hyaluronidase (HAse) activity is presented. It is based on the changes in viscosity and density during the enzymatic hydrolysis of hyaluronic acid (HA) by HAse. The variations of equivalent circuit parameters of piezoelectric quartz crystal (PQC) during the enzymatic degradation are discussed. The motional resistance shift curves indicate that the viscosity of the test solutions decreases during the hydrolysis process. The initial hydrolysis rates of HA are obtained from changes in viscosity and density as a function of incubation time. Kinetic parameters (the Michaelis constant K(m) and the maximum hydrolysis rate V(max)) of the degradation reaction are estimated by using a linear Lineweaver-Burk plot in this work. The K(m) was 0.44+/-0.03 mg.ml(-1) and the V(max) was -(5.29+/-0.36)x10(-3) kg.m(-2).s(-1/2).min(-1).     

Frequency response to liquid density of a piezoelectric quartz crystal sensor with longitudinal wave

Elimination of longitudinal wave effect is an important aspect in the detection cell design, although such consideration is ignored in most of references. Three detection cells were designed to investigate the influence of longitudinal wave effect on the frequency response of a piezoelectric quartz crystal (PQC) to liquid density. In the cell with horizontally mounted quartz crystal, the air/liquid interface acts the reflection surface for the longitudinal wave. The variation in liquid height by regent addition or solvent evaporation can result in fluctuation in the oscillating frequency of the PQC. The influence of the longitudinal wave is more obvious in a test liquid of lower density. In the cell with perpendicularly mounted quartz crystal, the longitudinal wave is mainly reflected back by the inner wall body. The fine structure of plotting of frequency shift (Δf) versus (ρη)^1/2 shows a wave shape, which is different from the well-known linear relationship between of Δf and (ρη)^1/2, where ρ and η are the density and viscosity of the liquid, respectively. And wave-shaped frequency-temperature curves were observed. The longitudinal wave was a kind of potential error source in the PQC measurements. The longitudinal wave effect can be efficiently eliminated by using a rough reflection surface. After eliminating the influence of reflected longitudinal wave, the stability of the sensor PQC was much improved.     

In Situ Monitoring of the Generation of Monodisperse Silica Particles during the Hydrolysis of Tetraethyl Orthosilicate with Piezoelectric Quartz Crystal Impedance Analyzer

The piezoelectric quartz crystal(PQC)impedance analyzer was used to monitor in situ the generation of monodisperse silica particles during the hydrolysis of tetraethyl orthosilicate (TEOS) and their adsorption onto and Au electrode in alcohol solutions containing water(6-15mol/L)and ammonia(0.2-2.0 mol/L).The equivalent circuit parameters,the resonance frequencies and the half-peak width values of the conductance spectra of the PQC resonance were obtained.The resonant frequency decreased notably while the motional resistance changed very slightly(within 1Ω during the hydrolysis reaction,suggesting that the mass effect dominated the adsorption of generated monodisperse silica particles on the gold electrode in this system.Changes in f0 indicated that the ammonia concentration affected the hydrolytic reaction obviously,and the influence of water concentration on the reaction was small while the water was significantly excessive.Kinetics of monodisperse silica particle adsorption occurring at the electrode i solution interface was analyzed using a first-order reaction scheme.In addition,the electrolyte-induced precipitation of the monodisperse silica of adsorbed particles per area and the converge of monodisperse silica particles were obtained from scanning electron nicroscope(SEM)observations.     

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.     

High sensitive piezoelectric quartz crystal liquid density sensor

<正>We report for the first time a cleavage phenomenon in the resonant peak of a piezoelectric quartz crystal(PQC) in liquid phase.In the presence of a strong longitudinal wave effect,an additional resonant peak appears in the conductance-frequency curve.With gradually increasing liquid density,the additional peak moves from low to high frequency region then disappears.The frequency of the additional resonant peak is sensitive to the change in liquid density.The frequency shift of the additional peak is linear with the liquid density in a given range.For a 5 MHz PQC with a reflection distance of 16 mm for longitudinal wave,the sensitivity to liquid density is 2.61×10~6 Hz g~(-1) cm~3.The overlap between the primary resonant peak and the additional resonant peak causes a decrease in the intensity of the former and an increase in the intensity of the latter.In a combined impedance analysis method,the changes in surface mass loading,density and viscosity of the liquid were monitored simultaneously by a PQC sensor.     

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.     

Adsorption studies of cationic starch onto quartz surface through an electrode-separated piezoelectric sensor

In the construction of an electrode-separated piezoelectric sensor (ESPS), the quartz surface is in direct contact with the liquid phase. The negatively charged quartz crystal surface can adsorb cationic starch. This adsorption process was in situ monitored from the frequency shift of the ESPS. It was shown that the adsorption of cationic starch onto the quartz surface is reversible with respect the dilution of the bulk phase. The adsorption behavior can be described by Langmuir model. The adsorption density and kinetics parameters were estimated from the frequency responses of the ESPS. The influence of pH and ionic strength on adsorption parameters was investigated. It was shown that the influence of pH on the adsorption rate was slight. With increasing ionic strength, the rate constants for adsorption and desorption increase, but the adsorption equilibrium constant and saturation adsorption density decrease. The adsorption equilibrium constant and adsorption density reach a maximum in buffer of pH 10.     

Piezoelectric transmission spectroelectrochemistry with a normal piezoelectric quartz crystal as an optically-transparent electrode

Piezoelectric transmission spectroelectrochemistry (PTSEC), i.e., the combination of electrochemistry and spectroelectrochemistry (SEC) with electrochemical quartz crystal microbalance (EQCM) technique is reported by using a normal piezoelectric quartz crystal (PQC) as an optically-transparent electrode (OTE). A theoretical relationship between the PQC response and the spectroelectrochemical response is derived and used to estimate the apparent molar absorptivity of the absorbing species deposited on the OTE on the PQC surface. The complex of copper with aspartic acid is used to test this new PQC-SEC technique. Results show that the combination of three such diverse techniques provides a very useful methodology for studying electrode processes and electrode surface characteristics in situ.     

Self-assembling of multi-jets by pyro-electrohydrodynamic effect for high throughput liquid nanodrops transfer

Destabilization of liquid film by electro-hydro-dynamics (EHD) pressure is achieved through the pyroelectric effect on a polar dielectric crystal. We show that by destabilizing the liquid film, periodical self-assembled multi-jets are obtained. The multi-jets operate simultaneously and could be exploited to dispense liquids with nanolitre drops. Such multiple self-assembled liquid jets have significant potential applicability for high-throughput liquid transfer by this novel pyro-EHD ink-jet approach. Since the method avoids the use of nozzles and electrodes, it is especially suitable for highly viscous liquids. Here we present and discuss the new multi-jet process and the results obtained with a liquid polymer (PDMS).     

Estimation of kinetics parameters for the adsorption of human serum albumin onto hydroxyapatite-modified silver electrodes by piezoelectric quartz crystal impedance analysis.

The adsorption of human serum albumin onto hydroxyapatite-modified silver electrodes has been in situ investigated by utilizing the piezoelectric quartz crystal impedance technique. The changes of equivalent circuit parameters were used to interpret the adsorption process. A kinetic model of two consecutive steps was derived to describe the process and compared with a first-order kinetic model by using residual analysis. The experimental data of frequency shift fitted to the model and kinetics parameters, k1, k2, psi1, psi2 and qr, were obtained. All fitted results were in reasonable agreement with the corresponding experimental results. Two adsorption constants (7.19 kJ mol(-1) and 22.89 kJ mol(-1)) were calculated according to the Arrhenius formula.     

Effect of the size of molecularly imprinted polymers sensing materials on piezoelectric quartz crystal sensor performance.

The effect of the size of the molecularly imprinted polymers (MIPs) on the piezoelectric quartz crystal (PQC) sensor performance was investigated. Erythromycin imprinted polymers microspheres with different sizes were synthesized by precipitation polymerization. The size of the MIPs was characterized by using transmission electron microscope (TEM) analysis. Being coated with a poly(vinyl chloride) (PVC) membrane containing MIPs, the proposed PQC sensor can selectively adsorb the template molecule. Investigation of the performance of sensors modified with different sizes of MIPs showed that PQC sensor modified with smaller size MIPs exhibited better performance and excellent selectivity. Other influencing factors on sensor functions modified with different sizes MIPs were also investigated.     

间苯二酚杯[4]芳烃为涂层的压电石英传感器测定液相多巴胺

研究了以间苯二酚杯[4]芳烃为敏感涂层的石英压电晶体（PQC）传感器,在中 性磷酸盐缓冲液体系中对神经传递质多巴胺和抗坏血酸的响应,发现间苯二酚杯 [4]芳烃对多能上能下胺有很好的响应选择性,这归因于间苯二酚杯[4]芳烃与多巴 胺分子结构相匹配,形成主客体超分子体系。以间苯二酚杯[4]芳烃为涂层的POC传 感器对液相中多巴胺具有响应快、重现性好、灵敏度高的特点,线性响应范围为3. 5-500 μg/g。     

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.     

Capillary bridges in electric fields

We analyzed the morphology of droplets of conductive liquids placed between two parallel plate electrodes as a function of the two control parameters electrode separation and applied voltage. Both electrodes were covered by thin insulating layers, as in conventional electrowetting experiments. Depending on the values of the control parameters, three different states of the system were found: stationary capillary bridges, stationary separated droplets, and periodic self-excited oscillations between both morphologies, which appear only above a certain threshold voltage. In the two stationary states, the morphology of the liquid is modified by the electric fields due to electrowetting and due to mutual electrostatic attraction, respectively. We determined a complete phase diagram within the two-dimensional phase space given by the control parameters. We discuss a model based on the interfacial and electrostatic contributions to the free energy. Numerical solutions of the model are in quantitative agreement with the phase boundaries found in the experiments. The dynamics in the oscillatory state are governed by electric charge relaxation and by contact angle hysteresis.