Sensors and Actuators B 92 (2003) 243254

Fullerene C60-cryptand coated surface acoustic wave quartz crystal sensor for organic vapors
Hung-Bin Lin, Jeng-Shong Shih
Department of Chemistry, National Taiwan Normal University, Taipei 116, Taiwan Received 24 October 2002; received in revised form 2 January 2003; accepted 14 January 2003

Abstract A fullerene C60-cryptand 22 (C60-di-propylamine-cryptand 22) coated surface acoustic wave (SAW) quartz crystal gas detection system with 250 MHz oscillator and a computer interface for signal acquisition and data processing was prepared to detect various organic vapors. The C60-cryptand 22 coated SAW quartz crystal sensor exhibited sensitivity to both polar and nonpolar organic molecules. The C60-cryptand 22 was demonstrated as a better and more sensitive coating material than fullerene C60 or cryptand 22 for polar organic molecules. Comparison of C60-cryptand 22 coated SAW crystal and quartz crystal microbalance (QCM) sensors was also made and the SAW sensor exhibited much better response than the piezoelectric sensor for organic molecules with the same concentrations. The C60-cryptand 22 coated SAW crystal sensor could be repeatedly reused for the detection of most of organic vapors, e.g. alcohols, aldehydes, ketones, ethers, alkanes and alkenes. The selectivity of the C60-cryptand 22 coated SAW crystal sensor for various polar organic vapors seem to be in the order: alcohols > aldehydes > ketones > ethers. For nonpolar organic molecules, the C60-cryptand 22 coated SAW crystal sensor showed sensitivity for alkenes, e.g. hexene and benzene than for alkanes, 1-hexane and cyclohexane. Effects of molar mass, steric structures and isomers of organic molecules on the SAW frequency responses were also investigated. The SAW detection system showed the good detection limit of 0.13.0 mg/ml for these organic molecules. The C60-cryptand 22 coated SAW crystal sensor was successfully applied as a quite sensitive gas chromatography (GC) detector for various organic compounds. The C60-cryptand 22 coated surface acoustic wave GC detector compared well with the commercial thermal conductivity detector (TCD) for various organic molecules, e.g. organic halides, alcohols, alkenes and ketones. 2003 Elsevier Science B.V. All rights reserved.
Keywords: Surface acoustic wave (SAW) quartz crystal sensor; Organic gas sensor; Fullerene C60; C60-cryptand 22; GC detector

1. Introduction Piezoelectric crystals, e.g. quartz and LiNbO3 , are well known to be sensitive to pressure on their surfaces [1]. In addition, the oscillating frequency of a piezoelectric crystal decreases on adsorption of a foreign substance onto its surface. The variation of oscillating frequency is proportional to the mass of foreign molecules deposited on the crystal surface and the basic frequency of the piezoelectric crystal. The theoretical detection limit of an oscillating quartz crystal has been reported to be as small as 1012 g for foreign molecules according to the Sauerbreys equation [2]: 2 F = 2.3 106 F0 Ms /A, where F (Hz) is the frequency shift due to the coating of the foreign molecules on quartz crystal, F0 (Hz) the vibrational frequency of uncoated quartz crystal, Ms (g) the mass of deposited coating
Corresponding author. Tel.: +886-2-29350749; fax: +886-2-29309077. E-mail address: jsshih@cc.ntnu.edu.tw (J.-S. Shih).

and A (cm2 ) the area coated. Piezoelectric crystals with appropriate coating adsorbents can be used as sensitive and highly selective gas/liquid sensors [38] for organic, metal ions and biological species. However, most of these piezoelectric crystal sensors are the bulk piezoelectric crystal sensors in which the vibrational wave propagated in the quartz crystal, from one side to another side surface, and use the 1030 MHz AT-cut quartz crystals. According to Sauerbreys equation, the frequency response ( F) can be increased with higher vibrational frequency crystals. However, higher frequency bulk piezoelectric bulk crystal (>100 MHz) is difcult to be prepared and not commercially available. Thus, the surface acoustic wave sensor with acoustic wave of 200400 MHz in which the acoustic wave on the surface of the piezoelectric crystal, launched and received on the same surface of the crystal [913]. The SAW sensor has demonstrated to be superior to the traditional piezoelectric crystal bulk sensor always called as quartz crystal microbalance (QCM) and the detection limit of SAW sensor have been reported to be as small as 1015 g

0925-4005/03/$ see front matter 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0925-4005(03)00159-X

244

H.-B. Lin, J.-S. Shih / Sensors and Actuators B 92 (2003) 243254

[1418] for analyte molecules. In this study, A C60-cryptand 22 coated SAW crystal detection system was prepared and applied to detect various polar and nonpolar organic vapors. Articial macrocyclic polyethers, cryptands and crown ethers, have demonstrated a remarkable complexing ability not only for metal ions [19,20], but also for polar organic species [21,22], e.g. amines, alcohols, aldehydes and ketones. Thus, in this study, cryptand 22 was used to adsorb and detect the polar organic vapors. However, cryptand 22 cannot adsorb nonpolar organic molecules, e.g. alkanes and alkenes. Fullerene C60 is a new allotropic form of carbon and its physical and chemical properties have recently received substantial attention [2325]. A characteristic feature of fullerene is its afnity to various organic molecules, especially nonpolar organic molecules. Therefore, in this study, fullerene C60-cryptand 22 was synthesized and applied as the coating material on the SAW crystal to adsorb and detect various nonpolar and polar molecules.

Fig. 1. Fullerene C60-cryptand 22 coated 250 MHz surface acoustic (SAW) sensor.

2.3. Apparatus A JASCO FTIR-5300 Fourier transform infrared (FTIR) was applied to identify synthesized C60-cryptand 22. The experimental set-up of the SAW quartz crystal detection system included an oscillator with a C60-cryptand 22 coated SAW quartz crystal obtained by Microsensor systems Co., USA, a frequency counter (Lutron FC-2700 Taiwan counter Co.), RS232 connected to a PC microcomputer and 500 ml glass working cell as shown in Figs. 1 and 2. A BASIC computer program was written for digital signal acquisition and data processing through RS232 to the PC microcomputer. The SAW-GC (gas chromatography) detection system a GC-14A gas chromatograph with a thermal conductivity detector and a Porapak Q 80/100 GC column for separation of various organic molecules was also set up as shown in Fig. 3.

2. Experimental 2.1. Preparation of C60-cryptand 22 coating material The coating material fullerene C60-cryptand 22 (C60-dipropylamine-cryptand 22) was obtained from the reaction between 7,16-bis (3-aminopropyl)-1,4,10,13- tetraoxa-7,16diaza cyclo-octadecane (di-propyl amine-cryptand 22) and fullerene C60. Di-propyl amine-cryptand 22 was synthesized as described by Chiou and Shih [7] and obtained as liquid product by the reaction of cryptand 22 (0.26 g, 1.00 mmol) with acetonitrile (5 mmol), followed by the reduction with borohydride and extraction with chloroform. Fullerene-cryptand 22 was obtained as a precipitate by adding the liquid product di-propyl amine-cryptand 22 and fullerene C60 (0.2 g, 0.276 mmol) to toluene (10 ml) and stirring at room temperature for 5 days. The solid product was cleaned with toluene and methanol several times to remove unreacted fullerene C60 and di-propyl amine-cryptand 22. The product was identied by FTIR with an absorption peak at around 1148 cm1 for the CN vibration. 2.2. SAW crystal coating The SAW quartz crystal plates with a basic resonant frequency of 250 MHz and the size of 8.0 mm 2.0 mm containing two-port IDTs (interdigital transducer) electrodes on one side of the SAW crystal plates that were obtained from Microsensor systems Co., USA. The SAW quartz crystals were coated with C60-cryptand 22/PVC (10 mg/10 mg) in 10 ml tetrahydrofuran (THF) solution by the spin coating with a microsyringe. After evaporation of the solvent, C60-cryptand 22 coated SAW quartz crystals were obtained.

Fig. 2. Experimental set-up of the C60-cryptand 22 coated SAW detection system.

H.-B. Lin, J.-S. Shih / Sensors and Actuators B 92 (2003) 243254

245

Fig. 3. Schematic diagram of the GC-SAW detection system based on C60-cryptand 22.

various organic vapors, e.g. alcohols, ketones, aldehydes, amines, alkane and alkenes, were investigated. As shown in Fig. 4, the 250 MHz C60-cryptand 22 coated SAW crystal sensor exhibited fairly good sensitivity for these organic vapors. Fig. 4 also reveals that the frequency of the C60-cryptand 22 coated SAW crystal sensor could be completely reversed after introducing pure N2 for desorption for various organic molecules except amines. The irreversible response for amines (Fig. 4d) may be attributed to probable chemical adsorption of amine molecules onto C60 of adsorbent C60-cryptand 22 as reported in the literature [25] while physical adsorption is found in all other organic vapors. This implies that the C60-cryptand 22 coated SAW crystal sensor can be repeatedly reused for the detection of most organic vapors, e.g. alcohols, aldehydes, ketones, ethers, alkanes and alkenes. 3.2. Comparison between SAW and QCM sensors It is well known that the piezoelectric crystals, e.g. quartz and LiNbO3, are applied as quite sensitive pressure sensors in both quartz crystal microbalance (QCM) and surface acoustic wave (SAW) detection systems. The comparison between SAW and QCM crystal sensors for ethanol

3. Results and discussion 3.1. Frequency response of C60-cryptand 22 coated SAW crystal sensor The frequency responses of the C60-cryptand 22 coated 250 MHz surface acoustic wave (SAW) crystal sensor for

Fig. 4. Frequency responses of the C60-cryptand 22 coated SAW sensor for methanol; (b) propyl aldehyde; (c) hexane and (d) propyl amine vapors.

246

H.-B. Lin, J.-S. Shih / Sensors and Actuators B 92 (2003) 243254

Fig. 5. Comparison between frequency responses of SAW and piezoelectric (PZ) crystal sensors based on C60-cryptand 22 (0.4 g) coatings for ethanol.

vapor with C60-cryptand 22 coating onto piezoelectric crystals was made. As shown in Fig. 5, the C60-cryptand 22 coated SAW crystal sensor exhibited a quite excellent sensitivity of approximately 750 Hz/(mg l1 ) for ethanol; in contrast, not quite good frequency response was found by using the C60-cryptand 22 coated QCM crystal sensor. This indicates that the C60-cryptand 22 coated SAW crystal sensor is a much more sensitive tool for trace organic vapor as compared with the traditional QCM sensors, although the noisy signal (ca. 10 Hz) of the SAW sensor is slightly greater than that of the QCM sensor (ca. 2 Hz).

3.3. Coating material effect The coating material effect on the frequency response of the SAW sensor was investigated. Various coating materials, e.g. C60, cryptand 22 and C60-cryptand 22 were used as adsorbents onto the SAW crystal plate to adsorb and detect methanol molecules. As Fig. 6 reveals, the SAW crystal with C60-cryptand 22 coating for methanol exhibits a signicantly better frequency response than C60 and cryptand 22 coated SAW crystals. It is not surprising for the least frequency shift of the C60 coated SAW crystal, because fullerene (C60) basically is an aromatic

Fig. 6. Effect of coating material on the 250 MHz SAW sensor for methanol (14 mg/l).

H.-B. Lin, J.-S. Shih / Sensors and Actuators B 92 (2003) 243254

247

Fig. 7. Effect of coating load of C60-cryptand 22 on the frequency response of the SAW sensor for ethanol (14 mg/l).

nonpolar molecule and cannot strongly adsorb polar organic molecules such as methanol. The quite larger frequency shifts of the C60-cryptand 22 and cryptand 22 coated SAW crystals may be due to hydrogen bonding formation between the macrocyclic polyether cryptand 22 and alcohol molecules. However, the enhancement of the frequency response by the attachment of C60 to cryptand 22 for C60-cryptand 22 may be attributed to the induction of the C60 molecule with 60 electrons to cryptand 22 which results in the strong adsorption of methanol onto the C60-cryptand 22 molecule and large frequency

response of the C60-cryptand 22 coated SAW crystal sensor. 3.4. Coating load effect The effect of the amount of C60-cryptand 22 coating on the frequency response of the SAW crystal gas sensor was also investigated for ethanol, as shown in Fig. 7. The SAW crystal with a thicker C60-cryptand 22 coating exhibited a larger frequency response for the same concentration (14 mg/l) of ethanol. However, the frequency response

Fig. 8. Frequency responses for (A) propanol; (B) propyl aldehyde and (C) acetone with the C60-cryptand 22 (0.4 g) coated SAW sensor.

248

H.-B. Lin, J.-S. Shih / Sensors and Actuators B 92 (2003) 243254

Fig. 9. Molecular mass effect of various alcohols on the frequency response of the C60-cryptand 22 coated SAW sensor: (A) butanol; (B) propanol; (C) ethanol and (D) methanol.

apparently tends to level off with larger amounts (>0.4 g) of C60-cryptand 22 coating. This behavior implies that there is a limit of the adsorption of gas molecules in a small area of adsorbent and an excessive coating is unnecessary for a SAW sensor. 3.5. Frequency responses for polar organic vapors The selectivity of the C60-cryptand 22-coated SAW crystal sensor for various polar organic vapors was also

investigated. Various polar-organic molecules containing the propyl group, e.g. propanol, propyl aldehyde and acetone, were detected via the C60-cryptand 22-coated SAW crystal sensor. The frequency responses of the C60-cryptand 22-coated SAW crystal sensor for these organic vapors appear to be in the following order (Fig. 8): propanol propyl aldehyde > acetone. This result may be attributed to the formation of the stronger hydrogen bonds, ROH O (cryptand 22) or ROH N (cryptand 22), between propanol and cryptand 22 than hydrogen bond

Fig. 10. Steric effect of butanol isomers on frequency response of the C60-cryptand 22 coated SAW sensor: (A) 1-butanol; (B) 2-butanol and (C) tert-butanol.

H.-B. Lin, J.-S. Shih / Sensors and Actuators B 92 (2003) 243254

249

Fig. 11. Isomer effect on frequency response of the C60-cryptand 22 coated SAW sensor for (A) n-butanol and (B) diethyl ether.

ROH HN (cryptand 22) between propyl aldehyde and cryptand 22, as well as the fact that there is no hydrogen bond formation between acetone and cryptand 22. 3.6. Effect of molar mass of gas molecules Various organic alcohols, e.g. methanol, ethanol, propanol and butanol, were detected by the C60-cryptand 22-coated SAW crystal sensor. As clearly shown in Fig. 9, the frequency shifts of the C60-cryptand 22-coated SAW crystal

sensor for these linear alcohols are, apparently, in the following order: butanol > propanol > ethanol > methanol. This result seems to indicate that a larger molar mass alcohol has a greater frequency response, which is consistent with the ndings in general reports for piezoelectric detectors [26]. It is reasonable to assume that, if the number of adsorbed molecules on an adsorbent is limited and is the same for various adsorbates, a greater molar mass of adsorbate would certainly lead to a larger frequency shift than in the case of a smaller molecule.

Fig. 12. Frequency responses of the C60-cryptand 22 coated SAW sensor for (A) hexene and (B) hexane.

250

H.-B. Lin, J.-S. Shih / Sensors and Actuators B 92 (2003) 243254 Table 1 Detection limits of various organic vapors with the C60-cryptand 22 coated SAW sensor Organic vapors Methanol Ethanol n-Propanol n-Butanol iso-Butanol tert-Butanol Detection limit (mg/l) 0.80 0.70 0.48 0.25 0.27 0.70 Organic vapors Diethyl ether Acetone Propionaldehyde Hexane Hexene Detection limit (mg/l) 3.60 2.60 0.85 2.30 0.80

3.7. Steric and isomer effects The steric effect of organic isomers such as butanol isomers was also investigated. The C60-cryptand 22-coated SAW crystal sensor for various butanol isomers was observed to be in the following order: 1-butanol > 2-butanol > tert-butanol (Fig. 10). This result may be attributed to the greater steric hindrance of tert- and 2-butanols than that of 1-butanol. This result seem to imply that a linear organic molecule like butanol has the smallest steric hindrance and the strongest adsorption on C60-cryptand 22 adsorbent, resulting in the best frequency response. Furthermore, the linear organic amine can be expected to be tightly, horizontally, adsorbed on the C60-cryptand 22 adsorbent surface, exhibiting a more effective pressure on the surface of the quartz crystal. This causes a greater frequency response than the partial vertical adsorption of the branched isomers onto C60-cryptand 22 of the SAW crystal sensor. Isomer effect of butanol and ether with same molar mass on the frequency response of the C60-cryptand 22 coated SAW crystal sensor was also studied. As shown in Fig. 11, much better frequency response for 1-butanol than that of diethyl ether was found, which may be attributed to the formation the hydrogen bonding between 1-butanol and C60-cryptand 22; in contrast, no possible hydrogen bonding was found between diethyl ether and C60-cryptand 22. 3.8. Frequency responses of non-polar organic vapors

accordance with the condence level desired. As suggested by Long and Winefordner [28], the use of k = 3 allows a condence level of 99.86% for a normal distribution of the blank signal. For example, the detection limit (CL ) for methanol can be estimated to be approximately 0.80 mg/l from the analytical sensitivity (m) of 73.2 Hz/(mg ml1 ) and the standard deviations of the blank signal (sB ) of 19.5 Hz with k = 3. The detection limits of C60-cryptand 22 SAW crystal sensor for various organic vapors are formulated in Table 1. The C60-cryptand 22 coated SAW crystal sensor obviously exhibited quite good sensitivity with the detection limits of approximately 0.23.0 mg/l for various polar organic vapors, e.g. alcohols, acetone, ether, aldehyde, and non-polar organic vapors, e.g. hexane and hexane. 3.10. Performance of GC-SAW detector

Because fullerene (C60) on C60-cryptand 22 adsorbent of the SAW sensor basically is an aromatic nonpolar group and therefore can be expected to adsorb and detect non-polar organic molecules such as 1-hexene and hexane. As shown in Fig. 12, the C60-cryptand 22 SAW crystal sensor exhibited quite sensitive response to 1-hexene. Furthermore, much better frequency response for 1-hexene than that of hexane was observed as shown in Fig. 12. This result may be attributed to the interaction between 1-hexene and C60, in contrast, no interaction between C60 and saturated hydrocarbons such as hexane. 3.9. Detection limit of the SAW sensor for organic vapors The detection limit of the C60-cryptand 22 coated SAW crystal sensor for various organic vapors was also studied. IUPAC [27] recommends that the detection limit of a detector (CL ) can be estimated as follows: CL = ksB m (1)

where sB is a standard deviation of the blank signal using factor 20 measurements, m the analytical sensitivity which can be estimated as the slope of the working curve as shown in Fig. 8, and k the numerical factor chosen in

The C60-cryptand 22 coated SAW crystal sensor was also applied as a gas chromatographic (GC) detector (denoted as GC-SAW detector) to detect polar and nonpolar organic molecules. The C60-cryptand 22 coated SAW detector was connected on line with a gas chromatograph as shown in Fig. 3. In this study, various organic molecules were separated using a Porpak packed GC column, and then were detected with the C60-cryptand 22 coated GC-SAW detector. As shown in Fig. 13, water and various organic molecules, e.g. ethanol, acetone, chloroform, ethyl ether and toluene, are separated with the Porapak GC column, and subsequently detected with the C60-cryptand 22 coated GC-SAW detector and a thermal conductivity detector (TCD). It can be found from Fig. 13B, that the SAW detector gives quite good responses with good sensitivity and good line shapes for these organic compounds. Compared with the thermal conductivity detector, the C60-cryptand 22 coated SAW detector seems to compare well with the more expensive commercial thermal conductivity detector for these organic molecules. The GC-SAW detector also was found to give good sensitivity and good line shapes for some non-polar organic molecules, e.g. n-hexane, cyclohexane and benzene (Fig. 14). The frequency response of the C60-cryptand 22 coated GC-SAW detector as a function of the concentration

H.-B. Lin, J.-S. Shih / Sensors and Actuators B 92 (2003) 243254

251

Fig. 13. Comparison of responses of water and various organic molecules with thermal conductivity detector (TCD) (A) and surface acoustic wave (SAW) GC detectors (B): (1) water, (2) ethanol, (3) acetone, (4) chloroform, (5) ethyl ether, (6) toluene.

Fig. 14. Frequency responses of the C60-cryptand 22 coated SAW gas chromatographic detector for n-hexane, cyclohexane and benzene.

252

H.-B. Lin, J.-S. Shih / Sensors and Actuators B 92 (2003) 243254

Fig. 15. Effect of concentration of acetone on (a) gas chromatogram and (b) the response of C60-cryptand 22 coated SAW gas chromatographic detector.

of the analyte, e.g. acetone, was found (Fig. 15a). The C60-cryptand 22 coated GC-SAW detector seems to exhibit a linear response to the amount of the analyte (Fig. 15b). This result implies that the organic compounds can be quantitatively detected with the C60-cryptand 22 coated GC-SAW detector. 3.11. Effects of ow rate and reproducibility of the GC-SAW detector The ow rate effect of the carrier gas (N2 ) on the frequency response of the C60-cryptand 22 coated GC-SAW detector for organic molecules C60-cryptand 22 coated GC-SAW detector was also examined. The increase in ow rate of the carrier gas was found to cause a decrease in the

frequency response of the GC-SAW detector for acetone as shown in Fig. 16. It is reasonable to assume that the slower ow rate easily leads to relatively complete equilibrium in the detector cell and maximum adsorption of the analyte molecules by the adsorbent C60-cryptand 22 on SAW crystal, resulting in a better frequency response of the C60-cryptand 22 coated GC-SAW detector. The reproducibility of the C60-cryptand 22 coated GC-SAW detector was also investigated with a series of 20 repetitive injections of acetone into the gas chromatograph with the SAW detector. The response of the C60-cryptand 22 coated GC-SAW detector exhibited a good reproducibility with a relative standard deviation (R.S.D.) of 4.2% (Fig. 17). The C60-cryptand 22 coated GC-SAW detector also demonstrated fast response and rapid return to the baseline.

H.-B. Lin, J.-S. Shih / Sensors and Actuators B 92 (2003) 243254

253

Fig. 16. Effect of ow rate of GC carrier gas N2 on the C60-cryptand 22 coated GC-SAW detector for acetone.

Fig. 17. Reproducibility of the response of C60-cryptand 22 coated SAW gas chromatographic detector for acetone with 20 repetitive injections.

4. Conclusion In conclusion, the fullerene C60-cryptand 22 coated SAW crystal sensor can be employed as a sensitive gas sensor for various organic vapors and exhibits much more sensitive tool for trace organic vapor as compared with the traditional QCM sensors. The C60-cryptand 22 coated SAW crystal sensor also could be successfully applied as a quite sensitive gas chromatographic (GC-SAW) detector for various polar and nonpolar organic compounds. The C60-cryptand 22 coated GC-SAW crystal detector seems to compare well

with the more expensive commercial conductivity detector for various organic molecules. The fullerene C60-cryptand 22 coated GC-SAW crystal detector also exhibited fast response and high reproducibility.

Acknowledgements The authors would like to express their gratitude to the National Science Council of the Republic of China in Taiwan for the nancial support.

254

H.-B. Lin, J.-S. Shih / Sensors and Actuators B 92 (2003) 243254 [18] J. Wagner, M. von Schickfus, Inductively coupled polymer coated surface acoustic wave sensor for organic vapors, Sens. Actuators B 76 (2001) 5863. [19] C.J. Pedersen, Cyclic polyethers and their complexes with metal salts, J. Am. Chem. Soc. 89 (1967) 70177036. [20] L.M. Kolthoff, Application of macrocyclic compounds in chemical analysis, Anal. Chem. 51 (1979) 1R22R. [21] D.J. Cram, Application of exchanger with crown ethers as anchor group in analytical and preparative chemistry, J. Chromatogr. 167 (1978) 307320. [22] S.S. Tsai, J.S. Shih, Application of the bifunctional switch-type cryptand ion chromatographic stationary phase for ion separation, Separation Sci. Tech. 33 (1998) 14071421. [23] H.W. Kroto, J.R. Heath, S.C. OBrien, R.F. Curl, R.E. Smalley, C60: Buckminsterfullerene, Nature 318 (1985) 162163. [24] W. Kraetschmer, L.D. Lamb, K. Fostiropoules, D.R. Huffman, Solid: C60, a new form of carbon, Nature 347 (1990) 354358. [25] Y.C. Chao, J.S. Shih, Adsorption study of organic molecules on fullerene with piezoelectric crystal detection system, Anal. Chim. Acta 374 (1998) 3946. [26] P. Chang, J.S. Shih, Preparation and application of cryptand-coated piezoelectric crystal gas-chromatographic detector, Anal. Chim. Acta 360 (1998) 6168. [27] L.A. Currie, Detection in Analytical Chemistry, ACS Press, Washington, DC, 1988. [28] G.I. Long, J.D. Winefordner, Limit of detection, a closer look at the IUPAC denition, Anal. Chem. 55 (1983) 712A724A.

References
[1] W.H. King Jr., Piezoelectric sorption detector, Anal. Chem. 36 (1964) 17351738. [2] G. Sauerbrey, The use of quartz oscillators for weighing thin layers and for microweighing, Z. Phys. 155 (1959) 206222. [3] W. Gopel, J. Hesse, J.N. Zemel, Sensors: A Comprehensive Survey, Weinheim, New York, 1989. [4] G.G. Guilbault, S.S. Lu, A.W. Czanderna, Application of Piezoelectric Quartz Crystal Microbalances, Elsevier, New York, 1984. [5] J. Janata, A. Bezegh, Chemical sensors, Anal. Chem. 60 (1988) 62R74R. [6] C.J. Lu, J.S. Shih, Detection of polar organic vapours with coated piezoelectric crystals based on crown ethers, Anal. Chim. Acta 306 (1995) 129137. [7] C.S. Chiou, J.S. Shih, Multifunctional cryptand coated piezoelectric quartz crystal detector for cations, Anal. Chim. Acta 392 (1999) 125133. [8] J.S. Shih, Piezoelectric crystal membrane chemical sensors based on fullerene and macrocyclic polyethers, J. Chin. Chem. Soc. 47 (2000) 2132. [9] R.M. White, F.W. Voltmer, Direct piezoelectric coupling to surface elastic waves, Appl. Phys. Lett. 7 (1965) 314316. [10] D.P. Morgan, Surface acoustic wave devices and application. Part I. Introductory review, Ultrasonics 11 (1973) 121131. [11] M.F. Lewis, Surface acoustic wave devices and applications 6, oscillators-the next successful surface acoustic wave device? Ultrasonics 12 (1974) 115123. [12] E.A. Ash, Acoustic Surface Wave, Springer, New York, 1978. [13] B.A. Auld, Acoustic Fields and Waves in Solids, 2nd ed., Wiley/Interscience, New York, 1973. [14] H. Wohltjen, Mechanism of operation and design considerations for surface acoustic wave device vapour sensors, Sens. Actuators 5 (1984) 307325. [15] H. Wohltjen, R. Dessy, Surface acoustic wave probe for chemical analysis. Part I. Introduction and instrument description, Anal. Chem. 51 (1979) 14581464. [16] H. Wohltjen, R. Dessy, Surface acoustic wave probe for chemical analysis. Part II. Gas chromatography detector, Anal. Chem. 51 (1979) 14651470. [17] D.Q. Li, M. Ma, Surface acoustic wave microsensors based on cyclodextrin coatings, Sens. Actuators B 69 (2000) 7584.

Biographies
Jeng-Shong Shih graduated from the National Taiwan Normal University with a BS degree in Chemistry in 1967, the National Ching-Hwa University with a MS degree in Inorganic Chemistry in 1970 and received his PhD degree in Analytical Chemistry from Michigan State University, USA, in 1978. He is currently a professor with the Department of Chemistry, National Taiwan Normal University. His research interests include chemical sensors, catalysts, surfactants, fullerenes and macrocyclic polyethers. Hung-Bin Lin received his MS degree in Analytical Chemistry from National Taiwan Normal University in July 2002. His research interest is the development of various SAW sensors.