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.     

Impedance and frequency characteristics of electrode-separated piezoelectric quartz crystals in liquids

The electrical equivalent circuit parameters of an electrode-separated piezoelectric quartz crystal (PQC), where the gaps between the electrodes and the crystal plate were filled with various liquids, were evaluated from admittance measurements and were compared with those of a normal PQC with Au electrodes adhering to the crystal plate. The resistance parameter in the equivalent circuit of the electrode-separated PQC was more sensitive to the specific conductivity, density and viscosity of liquids than was that of the normal PQC. This parameter, unlike that of the normal PQC, was also affecteded by the permittivity of the liquid. The effect of the liquid properties on the other parameters in the equivalent circuit and the series resonant frequency are also discussed.     

Different experimental results for the influence of immersion angle on the resonant frequency of a quartz crystal microbalance in a liquid phase: with a comment

This paper presents different experimental results of the influence of an immersion angle (θ, the angle between the surface of a quartz crystal resonator and the horizon) on the resonant frequency of a quartz crystal microbalance (QCM) sensor exposed one side of its sensing surfaces to liquid. The experimental results show that the immersion angle is an added factor that may influence the frequency of the QCM sensor. This type of influence is caused by variation of the reflection conditions of the longitudinal wave between the QCM sensor and the walls of the detection cell. The frequency shifts, measured by varying θ, are related to the QCM sensor used. When a QCM sensor with a weak longitudinal wave is used, its resonant frequency is nearly independent of θ. But, if a QCM sensor with a strong longitudinal wave is employed, the immersion angle is a potential error source for the measurements performed on the QCM sensor. When the reflection conditions of the longitudinal wave are reduced, the influence of θ on the resonant frequency of the QCM sensor is negligible. The slope of the plot of frequency shifts (ΔF) versus (ρη)^1/2, the square root of the product of solution density (ρ) and viscosity (η), may be influenced by θ in a single experiment for the QCM sensor with a strong longitudinal wave in low viscous liquids, which can however, be effectively weakened by using the averaged values of reduplicated experiments. In solutions with a large (ρη)^1/2 region (0-55 wt% sucrose solution as an example, with ρ value from 1.00 to 1.26 g cm⁻³ and η value from 0.01 to 0.22 g cm⁻¹ s⁻¹, respectively), the slope of the plot of ΔF versus (ρη)^1/2 is independent of θ even for the QCM sensor with a strong longitudinal wave in a single experiment. The influence of θ on the resonant frequency of the QCM sensor should be taken into consideration in its applications in liquid phase.     

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.     

Effect of the internal field on the IR absorption spectra of small particles in the case of 3D, 2D, and 1D size confinement

The spectral properties of composite materials based on small particles under 1D, 2D, and 3D size confinement are described using a combination of dispersive internal field and effective media theory approaches. Calculations performed for a number of crystalline materials have shown that the peak position and intensity of the vibrational band of the material under conditions of 1D, 2D, and 3D size confinement are changed, whereas the bandwidth of the band remains the same. In the case of 3D confinement, the peak position of the spectrum of isolated "mesoparticles" (epsilon(meso)(2)) appears to be very close to the intrinsic frequency of the lattice vibrations, calculated from the elastic constants of this crystal, as well as to the Fr?hlich's frequency. The largest shift (Deltanu) of the peak frequency, nu(max), from the bulk value is obtained in the case of 1D confinement when the peak position is practically coincident with the frequency of the longitudinal optical phonon (nu(LO)). These shifts are the result of intermolecular interactions, including both resonant and induced resonant dipole-dipole interactions.     

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.     

Numerical simulation of C/C/C planar X-ray waveguides.

A numerical simulation was done to check the possibility of using planar C/C/C multilayers with density contrast 0.2 and 0.7 g/cm3 as an X-ray waveguide. After an optimization procedure, suitable waveguide layer thicknesses were found which provide a high degree of resonant standing wave field intensity enhancement in the core layer at incident beam energy of 13 keV. The obtained results were compared with those of the Mo/Be/Mo waveguide, whose high waveguiding capability at the same energy value was reported in the 1990s. The comparison shows that standing wave field intensity resonant enhancement provided by C/C/C planar multilayers is very high and, consequently, a guided beam can be well detected.     

Construction and application of phenytoin anion-selective electrode based on bulk acoustic wave (BAW) sensing technique

This paper describes the construction of an anion-selective bulk acoustic wave (BAW) sensor for the direct determination of phenytoin sodium for the first time. Based on the sensitive mass response of a piezoelectric quartz crystal (PQC) and selective adsorption-desorption across the modified film, the BAW sensor was fabricated by coating a polyvinylchloride (PVC) film containing activator on one side of a PQC. The method was found to be sensitive, rapid and easy to handle without pretreatment of the sample. The logarithm of the frequency shift of the PQC shows a linear relationship to the logarithm of the concentration of phenytoin over the range 6.7 x 10(-8)-8.0 x 10(-4) M with a detection limit of 1.0 x 10(-8) M at pH 10.0. Recoveries were in the range 98.5-102.0%. Influencing factors were examined and optimized. Also discussed is the preliminary application of the phenytoin BAW sensor in serum and injection. The results for real samples obtained by the proposed method agreed with those obtained by conventional methods.     

Internally-referenced resonant mirror for chemical and biochemical sensing

The resonant mirror sensor is a planar optical sensor platform that uses frustrated total internal reflection to couple light into and out of a leaky waveguiding layer. The evanescent wave associated with the dielectric structure is very sensitive to changes in surface refractive index caused by the binding of macromolecules to immobilised proteins or other biorecognition species such as antibodies. However, such variations can also be generated by variations in the bulk analyte solution, via changes in the composition or temperature. In the device described here, an additional buried resonant mirror layer is incorporated into the sensor structure generating an internal reference resonant mirror. The efficacy of this internal reference system is demonstrated in both chemical and immunological systems--as a pH sensor monitoring the absorption of an encapsulated sulfonephthalein dye, and as a refractive index sensor measuring the adsorption of anti-protein A and binding of its corresponding antigen. In both cases the internally referenced resonant mirror provides a means by which errors due to fluctuations in light intensity, temperature and bulk composition may be accounted for.     

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.     

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.     

Dual quartz crystal microbalance compensation using a submerged reference crystal. Effect of surface roughness and liquid properties

Absolute resonant frequency measurements were made on gold-coated AT-cut quartz crystals with one face in contact with a series of liquids. The effect of surface roughness and liquid properties (viscosity and density) was analyzed in terms of a “trapped liquid” model. In this model, liquid present in surface imperfections is viewed as rigidly coupled mass. In some of the literature this density-dependent, but not viscosity-dependent, term is viewed as being additive to the hydrodynamic shift seen for a smooth surface. Data obtained using 1 μm and 5 μm surface finish crystals are inconsistent with the predictions of the trapped liquid model. This suggests hydrodynamic coupling between liquid internal and external to the crevices. Despite the lack of a theoretical model for the liquid motion, it is possible to compensate for frequency variations resulting from changing liquid properties and for roughness effects by making direct measurements of the resonant frequency difference between two crystals exposed to the same solution. This novel procedure works to the extent that the two crystals have similar surface topographies. Compensation is excellent for 1 μm finish crystals and good for 5 μm finish crystals.     

Direct observation of slow molecular relaxation by high-resolution light scattering spectroscopy

We developed a novel dynamic light scattering system to observe elastic relaxation phenomena with hyper frequency resolution. The principle of the measurement is based on the theory, which describes the dynamic structure factor of fluid under the condition of the frequency dependent compressibility. The dynamic structure factor, which is usually composed of the Brillouin and Rayleigh triplet, is modulated and shows an additional central component that directly reflects the whole aspect of the relaxation. In the experiment, the output from a frequency-doubled cw-YAG laser was incident into the liquid sample and the power spectrum of the light scattered into the backward direction was analyzed by the optical beating spectroscopy technique. The sample is liquid acetic acid that is known to show a strong ultrasonic relaxation around 1 MHz due to the molecular association process. We could find in the observed spectrum, the central component introduced by the phenomenon, whose relaxation frequency and the strength can be obtained from the width and the intensity of the observed central peak, respectively. The results show very good agreement with those previously obtained by the conventional ultrasonic spectroscopy technique.     

Contact angle dependence of the resonant frequency of sessile water droplets

The resonant vibrations of small (microliter) sessile water droplets supported on solid substrates were monitored using a simple optical detection technique. A small puff of air was used to apply an impulse to the droplets and their time dependent oscillations were monitored by passing a laser beam through the droplet and measuring the variations of the intensity of the scattered light using a simple photodiode arrangement. The resulting time dependent intensity changes were then Fourier transformed to obtain information about the vibrational frequencies of the droplets. The resonant frequencies of droplets with masses in the range 0.005-0.03 g were obtained on surfaces with water contact angles ranging from 12 ± 4° to 160 ± 5°. The contact angle dependence of the resonant frequency of the droplets was found to be in good agreement with a simple theory which considers standing wave states along the meridian profile length of the droplets.     

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).     

Field correlation effects on the resonant light scattering

Effects of incident photon field coherence on resonant light scattering have been investigated. In order to obtain the scattering intensity and the photon counting rate, an expression for the reduced density matrix for the scattered field has been derived. The expression involves the first-order correlation function of the incident field. The relation between the line shape of the scattered light and the bandwidth of the incident field has been clarified. Model calculations of the photon counting rate have been performed in the case of an incident field without first-order coherence. In our treatment, the transverse and longitudinal relaxation constants have been taken into account by using the impact approximation.     

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。     

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.     

Two-wave mixing on the cubic non-linearity in the smectic A liquid crystals

We present a theoretical study of two-wave mixing in smectic A liquid crystals (S_ALC) due to the resonant interaction of the electromagnetic (EM) waves through the second sound (SS), which is a new type of the cubic non-linearity. It is shown that a parametric amplification of one EM wave by the other occurs. Explicit expressions for the EM and SS wave amplitudes are obtained, which appear to be of the kink and transverse spatial soliton form, respectively. It is also shown that the SS wave creates flexoelectric polarization and space charge. The estimated gain is one or two orders of magnitude greater than the gain for the stimulated Brillouin scattering in isotropic organic liquids. The theoretical results obtained may be used as a basis for an experimental investigation of SS high frequency behaviour.     

Improve the signal-to-noise ratio of a quartz crystal microbalance in an impedance analysis method

A new data treatment method for the improvement of the signal-to-noise ratio of a quartz crystal microbalance (QCM) was proposed, where an averaged resonant frequency was calculated according to its conductance peak in an impedance analysis method. The relationship between the averaged resonant frequency and the medians of the conductance peak at different sampling heights was derived. It was shown that the signal-to-noise ratio of the averaged resonant frequency was about eight times of that of the resonant frequency calculated directly from its equivalent circuit parameters. The averaged resonant frequency of the QCM was applied to monitor the self-assembled process of a 6-O-(2′-(α-thiohydroxyacetamide)-ethyl)-diethoxylsilyl-β-cyclodextrin (OTED-β-CD), on gold surface as well as the adsorption of nitrophenol isomers onto the OTED-β-CD self-assembled monolayer film.