Selectivity acoustic mass sensors

Table 4.3 Selected values of acoustic impedances of materials used as electrodes in mass sensors...

Any of the methods of detection used in liquid chromatography can be used in IC, though some are more useful than others. If the eluent does not affect the detector the need for a suppressor disappears. Common means of detection in IC are ultraviolet (UV) absorption, including indirect absorption electrochemical, especially amperometric and pulsed amperometric and postcolumn derivatization. Detectors atomic absorption spectrometry, chemiluminescence, fluorescence, atomic spectroscopic, refractive index, electrochemical (besides conductivity) including amperometric, coulometric, potentiometric, polaro-graphic, pulsed amperometric, inductively coupled plasma emission spectrometry, ion-selective electrode, inductively coupled plasma mass spectrometry, bulk acoustic wave sensor, and evaporative light-scattering detection. 

The key feature of all acoustic wave sensors for detecting vapors is that measurable characteristics of the acoustic wave is altered as a result of adsorption on the surface of a receptive layer or absorption into the bulk of a thin layer (Figure 3). After sorption of the vapor by a thin film on top of the acoustic resonator equilibrium conditions are established and as a consequence of the increased mass or more accurately the change in the phase velocity of the acoustic wave a signal is created. Surface coatings generally enhance the sorption of vapors with the key properties of selectivity and sensitivity while affording reversibility. Typically, rubbery polymers were used on SAW devices such as polyisobutylene or substituted polysiloxanes but also self-assembled... 

The quartz-crystal microbalance (QCM) piezoelectric sensor operating system is based on interactions between thin organic layers, coated on the surface of a quartz crystal, and analytes. The ability of a QCM sensor to selectively recognize some molecules in a pomplex mixture depends on how selective and sensitive is the coated receptor. In order to obtain selective responses the coating of the quartz must be stable and capable of specific interactions with the desired analyte. Reversibility of the responses is another essential feature which requires to resort to weak interactions, since the formation of covalent or ionic bonds would lead to irreversible saturation of the sensitive layer. On the other hand pure dispersion forces are unsuitable due to their aspecificity. Sensitivity in mass sensors depends mainly on the transduction mechanism employed. Surface acoustic wave devices (SAW) are usually at least two order of magnitude more sensitive than QCM ones with the same coating. 

The relative importance of the mass-loading and viscoelastic contributions to the observed acoustic sensor response is an issue that has yet to be resolved. Capitalizing on these effects to improve chemical selectivity and detection sensitivity requires further characterization of sensor response, in terms of both velocity and attenuation changes, in addition to more accurate models describing how coating-analyte interactions affect relevant film properties. 

As the readers may see, quartz crystal resonator (QCR) sensors are out of the content of this chapter because their fundamentals are far from spectrometric aspects. These acoustic devices, especially applied in direct contact to an aqueous liquid, are commonly known as quartz crystal microbalance (QCM) [104] and used to convert a mass ora mass accumulation on the surface of the quartz crystal or, almost equivalent, the thickness or a thickness increase of a foreign layer on the crystal surface, into a frequency shift — a decrease in the ultrasonic frequency — then converted into an electrical signal. This unspecific response can be made selective, even specific, in the case of QCM immunosensors [105]. Despite non-gravimetric contributions have been attributed to the QCR response, such as the effect of single-film viscoelasticity [106], these contributions are also showed by a shift of the fixed US frequency applied to the resonator so, the spectrum of the system under study is never obtained and the methods developed with the help of these devices cannot be considered spectrometric. Recent studies on acoustic properties of living cells on the sub-second timescale have involved both a QCM and an impedance analyser thus susceptance and conductance spectra are obtained by the latter [107]. 

There are some excellent review articles on different aspects of mesostructured materials, such as synthesis, properties, and applications. " Extensive research effort has been devoted to the exploitation of new phases (lamellar, cubic, hexagonal structures), expansion of the pore sizes (about 2-50 nm are accessible), and variable framework compositions (from pure silica, through mixed metal oxides to purely metal oxide-based frameworks, and inorganic-organic hybrid mesostructures). Another research focus is on the formation of mesostructured materials in other morphologies than powders, e.g. monolithic materials and films, which are required for a variety of applications including, but not limited to, sensors (based on piezoelectric mass balances or surface acoustic wave devices), catalyst supports, (size- and shape-selective) filtration membranes or (opto)electronic devices. The current article is focused... 

In the area of chemical sensors, thin polymer films are routinely used as coatings for the semi-selective sorption of chemical vapors. One sensor technology, the surface acoustic wave (SAW) device, has demonstrated excellent sensitivity as a vapor sensor when coated with films having appropriate solubility properties (2). To date, most sensor applications have utilized the extreme mass sensitivity of the devices. In this paper, we will examine the response mechanisms of the SAW sensor and demonstrate its sensitivity to changes in the elastic properties of the coating materials. Finally, we will discuss the significance of these results in terms of current sensor applications, and the advantages of the SAW for polymeric materials characterization. 

Vapor sensor based on SAW devices were first reported in 1979, most of them rely on the mass sensitivity of the detector, in conjunction with a chemically selective coating that adsorbs the vapor of interest and result in an increased mass loading of the device [5]. In its simplest form SAW sensor consists of a delay line, which consists of an IDT at each end of an appropriate piezoelectric substrate. One IDT acts as transmitter and other acts as the receiver of acoustic energy which travels along... 

The nature of acoustic waves generated in piezoelectric materials is determined by the piezoelectric material orientation as well as the metal electrodes configuration employed to generate the electric field that induces acoustic waves by converse piezoelectric effect. As gas sensors, the resonators are coated with layers which selectively absorb or adsorb analytes of interest and thereby induce a mass change that is then detected via a shift in the resonant frequency of the device (Kurosawa et al. 1990). The detection limits and the relative (5) mass sensitivities for different types of acoustic sensors are presented in Table 13.1. The comparison of various types of AW sensors is also presented in Table 13.2. Several books and reviews (Ballantine et al. 1997 Ippolito et al. 2009) provide a more detailed analysis of AW-based sensors operation. 

Operation of a SAW device as a chemical sensor normally involves the deposition of some chemically selective material onto the surface of the SAW device (2-5). In this work thin polymer films are coated over the entire surface of the SAW device. When a vapor is exposed to the polymer-coated SAW device, it distributes between the gas, bulk polymer phase, and interfaces, and comes to rapid thermodynamic equilibrium. Changes in mass and modulus that result from vapor absorption poturb the propagation of the surface acoustic wave (6), and ordinarily result in a r uction of the observ resonant frequency. The ratio between the concentration of the vapor in the gas phase, Cy, and the concentration of vapor in the polymer phase, Cp, is known as the partition coefficient, Kp, given by equation 1. The portion of the... 

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