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38723182 New Electrochemical Sensors

38723182 New Electrochemical Sensors

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ANALYTICAL PROCEEDINGS, NOVEMBER 1991, VOL 28

New Electrochemical Sensors
The following are summaries of eleven of the papers presented at the Joint Analytical/ Faraday Symposium at the Annual Chemical Congress of the RSC held on April 8th-I2th, 1991, in Imperial College, London.

Solid-state Gas Sensors: Prospects for Selectivity
Downloaded by University of Missouri-Columbia on 21 September 2010 Published on 01 January 1991 on http://pubs.rsc.org | doi:10.1039/AP9912800366

David E. Williams Department of Chemistry, University College London, 20 Gordon Street, London WCIH OAJ

Metal oxides, such as tin dioxide and zinc oxide, fabricated either in the form of thin (=lo0 nm) films or as thicker porous bodies, show an electrical conductivity at temperatures of about 300°C which is very sensitive to the presence of trace amounts (ppm level) of reactive gases (hydrocarbons, hydrogen, carbon monoxide, methane, ammonia, oxides of sulphur and nitrogen, chlorine, hydrogen sulphide) in air. This phenomenon has been exploited for many years in warning devices. Most commercial elements utilize porous, thick (==lo0 pm) films of tin dioxide. Typically, the layer might be deposited onto the outside of a small alumina tube by successive dipping into a tin salt solution and thermal decomposition. A heater is threaded into the centre of the tube. These devices are simple, robust and inexpensive. They are, however, if anything, too sensitive to too many things, although a certain degree of selectivity can be obtained by control of the operating temperature. The question is, therefore, whether, by choice of oxide material or some other means, selectivity can be enhanced. 1,2 M ~ r r i s o n , in discussing this question, has ~ pointed out that although the gas sensing phenomenon appears to be intimately connected with the occurrence of a surfacecatalysed combustion, the notion of selectivity in a gas sensor is different to that of the apparently related notion of selectivity in a catalyst: for a catalyst, selectivity means a bias in favour of a particular reaction product, whereas for a sensor it means a bias in favour of a particular reactant, often in a complex mixture of potential reactants. As far as the second part of the question is concerned, it has been pointed out' that the surface-catalysed combustion causes a gradient in the composition of reactant and product gases throughout a porous sensor structure, and that this can be used to build in a degree of selectivity based on the differing reactivity of different gases. Hence, in a sufficiently thick structure, the outer layers of the device act as a kind of filter, burning away the more reactive gases and leaving only the less reactive gases to affect the conductivity in the vicinity of electrodes buried within the structure. There seems to be plenty of scope for using this kind of idea, the alteration of relative response by alteration of the geometry of the sensor layer and of the measuring electrodes, to develop tailored devices. In order to address the first part of the question, an experimental programme was carried out2 to investigate the response of several hundred different oxides to a range of gases. Table 1indicates the range of materials investigated; the gases studied were: hydrogen, carbon monoxide, methane, propane, ethene, ammonia, hydrogen sulphide, nitrogen dioxide, sulphur dioxide and chlorine, and changes in oxygen partial pressure. The first conclusion of this work was strikingly simple: most oxides respond to most gases. A few materials showed selectivity to some gases, most often ammonia and

Table 1 Range of materials investigated

Perovskite-type compounds of tin Al - ,B,Snl - .CXO3Ca, Sr, Ba Ca, Sr, Ba, Pb La, Y, Gd Fe, Co Ti, Zr, Ce

Pyrochlore-type compounds of tin
A2 - ,B,Sn2 - xCx07 Specific examples: CaSnTi207 CaCeSnzO7 Gd2Sn207 La2Sn207
y2sn207

A

Niobates Bronzes Al - xBxNb206 Examples: A, B-Pb, Ba, Sr A6BxNblO- x o 3 0 Example: Bi6Fe4Nb6030

B

C

Bi2Sn207 Transition metal compounds Fe, Co, Ni, Cu niobates

Tantalates Specific examples: BaSn03 BaSn0.5Ti0.503 BaSn0,9Zr0,103 2 BaSnO.8FeO. 0 3 Ba0.9Gdo.1Sn03 FeTa04 CoTa206 NiTa206 CUTa206

hydrogen s ~ l p h i d ebut this was the exception rather than the ,~ rule. A second conclusion was that there was a clear rz-typelptype classification of the oxides, even in the absence of a response to varying oxygen partial pressure, and correspondingly a classification of the gases into oxidizing and reducing agents. Exceptions to this classification stood out clearly: Table 2 shows a part of it, in which the response has been coded simply in terms of its sign. The interpretation is that, in general, the response of oxides to gases, being a change in the concentration of the charge carriers giving rise to the conductivity, is controlled by the surface concentration of a single, reactive surface species, common to all oxides and presumed (following studies on tin dioxide and zinc to be an oxygen ion, 0 2 - 0-. Response mechanisms have been fully , discussed elsewhere ,13235and, indeed, a model simply rationalizing the exceptions in the classification can be constructed.6 The answer, therefore, to the first part of the question posed above is that very strong selectivity seems rather rare, being confined to a few materials and a few gases: if a generalization is required, in the study these were those gases (NH3, H2S) that could be considered to act as Lewis bases on materials in which it is presumed that oxygen surface species were unreactive at the measurement temperature. On the other hand, there was sufficient variation in the relative magnitude of the response of different materials to different gases to allow ample scope for the strategy of using arrays of differently responding sensors to resolve the composition of mixtures.

Semiconductor Gas Sensors and Selectivity Gary S. and Kohl. S. A. However. Actuators. ed. VOL 28 367 Table 2 Classification of materials and responses: the response is coded simply by the sign of the resistance change on exposure to the gas. ch. E.org | doi:10. 1990. Bristol and Philadelphia. T.. Moseley. responding to a wide range of reducing gases. T.lFe03 La6W012 NdzZ1-207 Y2BaZn05 + + + + + + + + + + + + + + + + + + + + - + + + - + References 1 Williams. Sens. J. showing opposite sign of response to oxidizing and reducing gases stand out clearly. Tokyo and Amsterdam.7%) NH3 so2 H2S (0. initially based on zinc oxide but now usually based on the n-type semiconductor tin dioxide. 6 Williams.. except for the first listed. Bristol and Philadelphia. operating a sensor at =300 "Cgave a For device sensitive to the presence of carbon monoxide but 0 2 4 6 [Gas] (lo3 ppm) Fig.1%) Cl2 NO2 Downloaded by University of Missouri-Columbia on 21 September 2010 Published on 01 January 1991 on http://pubs. Adam Hilger. Moseley. J.9CaO. it is the problem of selectivity that is addressed in this paper. Volume I . 1988. A plus sign indicates a resistance increase with respect to the value in air. Swansea SA2 8PP The resistance of certain semiconductor materials has been known to change in the presence of reducing gases since the early 1950s. E. Coles Department of Electrical and Electronic Engineering.View Online ANALYTICAL PROCEEDINGS. 5 and Tofield. B1. pp.W. Muter. 3 Morrison. P. eds. 1991. D. 1987.. and Norris. a minus sign indicates a resistance decrease. In all atmospheres. low power consumption and cost.rsc. eds. V. E. Chem. despite the fact that they can possess many of the characteristics desirable in a gas sensing device.^ Early sensors received a great deal of criticism as they tended to be irreproducible and have poor selectivity. 2 Moseley. G.. R. D. 0. the gases are introduced as mixtures (1'70 except where stated) in air Material Low 0 2 (100PPm) c4 H co H2 C2H4 (0. Williams. 12. 4 Moseley. in the press. Actuators. Heiland. Seiyama. 15-38. B.. C. Effectively p-type oxidesSr(SrNb)0 3 LiFeSn04 Y2Ti20 BaTi03 SrTiO3 LaO. E.. It might also be true that industry and commerce expected too much of this type of sensor. 71-123. pp. University of Wales.1039/AP9912800366 2. T. 1 Variation of conductivity with gas concentration for a hydrogen-selective sensor in hydrogen and carbon monoxide . 113. Exceptions to the general n-typelp-type classification of materials. T. T.. P. M. P.. D... and Moseley. fast response speed.^.. NOVEMBER 1991... D. Stoneham.. in Chemical Sensor Technology.~ example. P. D.... Sens. P. 1987. including high sensitivity.. Techniques and Mechanisms in Gas Sensing. Gas sensors exploiting this observation. 425. 14 v) m $ B 10 6 2 Selectivity in Tin Dioxide Gas Sensors Early workers in this area discovered that operating tin dioxide sensors at different temperatures conferred a degree of ~electivity. Kodansha and Elsevier. in Solid State Gas Sensors. and Williams. and Williams. have been available commercially for some two decade^. 4. D. T. E. Adam Hilger.

Anal. Fukiishi. These devices showed remarkable characteristics as shown in Fig.. Br. and many other types of sensor. 17. A maximum sensitivity is observed at an operating temperature of =250"C. N.. gave a device sensitive to the presence of the lower hydrocarbons but insensitive to the presence of carbon monoxide. and Knop. gave a sensor with the opposite selectivity. As a control. but fired at higher temperatures. T. 4 Taguchi. carbon monoxide and hydrogen. . Initial work at Swansea produced two selective sensors.. H. 1970. J. J. 1991.. 1280809. S. Watson. It is known that bismuth oxide and tin dioxide undergo a solid-state reaction above -600 "C producing bismuth stannate. Kato. and ( c ) 175"C insensitive to the presence of methane. 89. NOVEMBER 1991. Stand. Bi2Sn207. Chem. J. . A second sensor.. 1. Sensors produced from these materials in an analogous way to the tin dioxide-bismuth oxide sensors. 1968. V. sensors were also produced from pure tin dioxide fired at 1500°C. 1985.. 138. which has a pyrochlore structure. J. T. and Gallagher. p. 5 Firth. Can.. F.' In our sensors all of the bismuth oxide reacts and the final sensor element is composed of bismuth stannate and tin dioxide only. . Chem. A. G. References 1 Brattain. 1954.. 7. These sensors are selective throughout the viable operating temperature range. The exact reasons for these observations are as yet not fully understood but are currently being studied and will form the basis of a subsequent paper. V.. 1953. aluminium silicate and palladium chloride. 56... O. Above a concentration of =17% m/m Biz03 the response to CO also begins to fall and this reaches zero above -23% m/m. 459. 6 Coles. 1974. Pat. Sens.View Online 368 ANALYTICAL PROCEEDINGS. 2. IERE Conference Proceedings. However.. 7 Coles.1039/AP9912800366 0 5 10 0 5 10 0 5 10 [Gas] ( l o 2 ppm) Fig. 2 Heiland. Tech. G. Although the term selective has been used. J. Williams. Environmental Sensors and Applications. 9 Brisse.9 These were also studied in the hope that they would yield new selective sensors and further elucidate the properties exhibited by these devices. being typically in the region of 1500 "C. Producing a sensor with the opposite selectivity required the addition of =l% platinum to the oxide and operation at a higher temperature of -600 "C. the response to hydrogen is observed to persist undiminished until this also begins to fall to zero above -25% m/m.org | doi:10. formed by the sintering of tin dioxide and bismuth oxide. M . 1288009..rsc. In an attempt to understand the properties exhibited by these sensors the carbon monoxide selective device was studied in more detail. Actuators. There are several other stannates of general formula M2Sn207 which also possess the pyrochlore structure .. Actuators. as bismuth oxide is added the response to methane rapidly diminishes. 1282993. Natl. 2. prepared from tin dioxide. At low operating temperatures (-175 "C) the device shows no response to carbon monoxide or methane but exhibits an increase in resistance in the presence of hydrogen as would be expected in a p-type material. J. Tin Dioxide-Bismuth Oxide System Tin dioxide itself exhibits conductance changes in the presence of many reducing gases.. A. An immediate difference is the high temperatures required to produce these other stannates . Phys. B3. Res. showed various degrees of selectivity and sensitivity but none compared favourably with the original devices. and Jones. 7 . 1502. Conclusions It is possible to produce tin dioxide based sensors with marked selectivity towards the common toxic and/or flammable gases methane. Jones. and Smith.. below which resistances become excessively high and surface reactions too slow. in reality these sensors. In the production of these sensors the oxide mixture is fired at 800°C. J. ( b ) 280. a conventional response is observed in the presence of hydrogen but a resistance increase is observed in the presence of carbon monoxide.. 8 Roth. J . falling to zero at -15% m/m. G. 3 Seiyama. 859. It is also possible to produce a single sensor in which the selectivity and mode of operation can be switched and tuned by modulation of the operating temperature. A . G.6 The first. . 1962. 1956. At high operating temperatures ( ~ 4 0 "C) the sensor shows 0 conventional decreases in resistance in the presence of all three gases as would be expected for this n-type material. VOL 28 25 Downloaded by University of Missouri-Columbia on 21 September 2010 Published on 01 January 1991 on http://pubs.. S. will also respond to certain other gases. Bur. notably hydrogen.. When the Bi203 content of these devices is increased above that at which the carbon monoxide response has fallen to zero. Bell Syst. . and Nagatini.. The response to carbon monoxide remains unaltered. 46. W. above which conductivity by thermal excitation obscures the changes produced by the presence of a contaminant gas). as shown in Fig.^ A remarkable feature of this sensor is its linear change in conductance with increasing gas concentration even up to several thousand ppm. 2 Resistance versus contaminant gas concentration plots for a sensor fabricated from Sn02 pre-sintered at 1500 "C in air and maintained at three different operating temperatures: ( a ) 400.. The optimum composition of this sensor is therefore 8345% m/m S n 0 2: 1517% m/m Bi203. K.32. B. 34. The notable feature of these sensors is that the selectivity is observed throughout the viable operating temperature range (between =150 "C. At intermediate temperatures (-280 "C) no response is observed for methane.. K. G . and -700 "C. Sensors of this type usually tend towards saturation at such high levels. and Bardeen.1. It is therefore possible to produce a third sensor which is sensitive to the presence of hydrogen but shows no resistance changes in the presence of carbon monoxide or the lower hydrocarbon^. Sens. 57.

. such as the sulphate-zirconia interface can be used as sensing elements. Siebert... E. Amsterdam. involve two main types. Gros. 151-171. There is much less information available on the receptor sites for anions. Newcastle upon Tyne NEI 7RU The availability of crystal structure information on biological receptor sites’ for metal ions has provided a blueprint for the design of synthetic receptor molecules. many of which have provided analytical reagents for sensors. an efficient ionic anchoring does not require that the counter ion of the species to be analysed be the predominant ionic ~ a r r i e rCatalysts known to be active . in Fast Ion Transport in Solids.. while the potassium goes into the ether cavity. this latter condition implies that the electron conduction associated with the redox system is not very high. .rsc. NOVEMBER 1991.^ Basic Design We used another approach with the intention of building a receptor site which would have an induced fit to anions of choice. Soc.. Elsevier..org | doi:10. M. Tokyo and Amsterdam. Siebert.. and hydrophobic interactions. if one N-H on each nitrogen points into the cavity of the ring..6 Generally. J. 1991.. W. and Kleitz.. the transition to the peroxide reduction can result in shorter response times. Pelloux. 5 . VCH Weinheim. ed. A straight comparison of the coordination of 18-crown-6 to potassium ions with the coordination of hexaprotonated l8-aza crown-6 to chloride ions indicates that the ion-dipole interaction of the crown molecule has no direct analogue in the second situation. Fouletier. 343. 1976. M. and Kleitz. J. As in aqueous electrolytes. A . . Fouletier. Appl. as at present understood. Seinezia. in Chemical Sensor Technology. M. H. a sensitive surface must be ionically anchored to the electrolytic reference and must exhibit a redox reaction which equilibrates rapidly with the species to be analysed. separated by a linking group. At low temperatures. the other apparently constructed without the obvious Coulombic interactions. J. Seiyama. J.’ These functions can be separated to a large extent which has not yet been fully explored. Electrochem. This is also true of the conventional ion-sensitive electrodes and of the Nasicon membrane5 investigated for Na+ sensing. Quessada. the other must point outwards. Natural strategies for anions.’ and the second in the sulphate receptor protein2 of Salmonella typhimurium. Actuators. The University of Newcastle upon Tyne.. France Downloaded by University of Missouri-Columbia on 21 September 2010 Published on 01 January 1991 on http://pubs.. pp. LIESG/ENSEEG. P. will sandwich potassium cations. J. Fabry. M. Kleitz. P. for example.8 References Kleitz. M. 1. J . 15. The synthetic approach to coordinating anions essentially turns the inorganic chemist’s ideas of coordination inside out. J. A good transmission line is composed of elements through which the electrolytic reference is constant and possibly interphases where the electrolytic reference steps are well defined by local chemical buffers. Therefore. Macrocycles which are oligomers of ethyleneimine also tend to have the nitrogens anti on each ethane segment and to have a large open cavity..1039/AP9912800366 Solid-state potentiometric sensors can be described as being composed of sensitive surfaces and an electrolytic reference transmission line... 1979.. Kodansha Elsevier. 1989. . 33. P. In fact the chloride binds exo3 to the ring. Electrochem. Sens..2. SOC. an additional potential-collecting compound must be suitably incorporated. causing the deliberate synthesis of thousands of new molecules. T. J. Electrode reactions. J. pp. Domaine Universitaire. Million-Brodaz. P.. and Kleitz. The first type is found in proteins which bind to DNA. P. In each instance the receptor site is a close fit to the contours of the anionic substrate. The differential zirconia sensor. 1980. M. and thence more suitable for coordination to anions. Some of these interphases. 204. A. Fabry. Fouletier. VOL 28 369 Novel Solid-state Potentiometric Sensors Michel Kleitz Laboratoire d’lonique et d’Electrochimie des Solides de Grenoble. Hesse. Kleitz. Vashishta. whether achieved by perfect size match or by induced fit. E. It has been demonstrated with 02*and 02-that a catalysed partial redox reaction can give better sensor performance than a conventional complete reaction. .~ for the species to be analysed can also be good candidates for the redox function. and Zemel. V O ~ ... BP 75. 1988. 1. 1573. Fabry. anions are found inside the cavity of polyaza macro cycle^. Electrochem. and Gauthier.. M. eds. eds. M.. 123. 177. Pelloux.. In some crystal structures. 1987. It is also noteworthy that polyamines in which the linkers have three or more methylene links between nitrogens (such as the biological amines spermidine and putrescine) are much more basic than the ethylenediamine oligomers ubiquitous in inorganic chemistry. in the press. J ... in the conventional electrochemical sense.View Online ANALYTICAL PROCEEDINGS. Design and Synthesis of Receptors for Sensor Use Joyce C. J . as the directional force. In order to be of interest. and Kleitz. F... J . and Kleitz. Lockhart Chemistry Department. and Siebert... and Fouletier. Solid State lonics. et al. N. Fabry. P. 1975. one using sites of opposite charge (provided principally by the proximity of protonated Arg and Lys residues) with hydrogen bonding as a directional force.. in that instance hydrogen bonding. Fouletier. E.. 69-73. are the natural choice. 38402 Saint Martin-d’Heres. Molecules containing two crown ether moieties. Gopel. 134. in Chemical and Biochemical Sensors.2 the zirconia-tip sensor3 and the sulphate-zirconia contact4 illustrate the different behaviour of such interphases. M.. is unlikely to involve as many as six interactions to chloride simultaneously.

J. resulting in an increase of the marker ion penetration to the electrode. E.-M. and Mertes. C. Lehn. and Mertes. Kennard.-M. Hosseini.. 1971.* These devices were based on Langmuir-Blodgett deposition of multilayers of acidic lipid membranes on glassy carbon electrodes. Vigneron. J. Am. Cullinane. 7133. Hosseini. Am.-M. M. SOC. J. and Zompa. and to Dr. A synthetic route. More than three layers of lipid were necessary to block the permeation of Fe(CN)64-. Brice. Erindale Campus. Dr. Jagur-Grodzinski. 104. NOVEMBER 1991.Dalton Trans. Commun. 2331. Arafa and D... K. T. which was used as a marker ion.. W. Helv. will be described elsewhere. Ontario L5L IC6.6. O.. linker was formed from a polyamino residue. Z. 1977. Lehn. 1) were shown by ‘H NMR to sandwich potassium ions. small cyclic polyamines (four nitrogens) were more likely to interact with the terminal y phosphate only. a change in the alignment of the lipid occurred on the glassy carbon surface owing to electrostatic complexation of calcium ions with acidic phosphate head groups of the lipids. The 31P shifts observed for 1 : 1 ratios of polyamine to ATP were shifted for these situations in accordance with this prediction. R. 112. Handyside.P. A further extension of artificial lipid membranes for electrochemical sensing was the construction of ‘biomimetic ion-channel sensors’.. 1983. Gelb.2454.. Nature (London). and Tasumi. Lehn. The bis(crowns) (I) (Fig. M. M. 93. R. D. Chem. Lockhart. N. Williams. VOL 28 X = polyaza Fig. Stephen Brown. B. 1982.. J. Z.. 314. while a slightly longer chain.... J. McDonnell. protonated conformation was an excellent sideways fit to the phosphates of a triphosphate chain. 66. Thanks are due to the SERC for financial support. 535. J. and the separation and characterization of the bis(crowns) (I) .7 Molecular graphics studies indicated that diethylenetriamine in the extended. References Brookhaven Protein Data Bank. Kinnear. Discussion Adenosine triphosphate (ATP) is a favourite anion for complexation studies. P. M. E. J.. 257.. Rodgers. J.. John D. M. SOC. to show that the coreceptor is clearly binding potassium ions plus counter ions simultaneously. could wrap simultaneously round the y and residues. J... T. Krull. Luz. hormonereceptor and avidin-biotin interactions have been monitored by observation of the transmembrane ion current. L. An important advantage of such an electrochemical sensing system is the increased sensitivity which is derived from an intrinsic amplification process.. which are shifted relative to those of the free ATP in solutions containing receptor in a suitable mole ratio to the ATP. Biol. Chim. 1982. the first multi-receptors to exhibit multiple binding to cation and counter ion simultaneously. J.. P. N.. Chem.. G. J. In the presence of the stimulant Ca2+. Acta.. and Quiocho.. Meric.. Mousley for their help in this project. Suitable receptors for the phosphate residues have been detected previously by examining the timeaveraged 31P NMR signals for the a. Kallury Chemical Sensors Group. Margulis.. Brennan.. Helv. Chem. SOC. A single selective binding event between a receptor and a target molecule can result in an increase of the transmembrane conduction that involves thousands of ions. 3359 Mississauga Road North.. W. lectin-saccharide . it should be capable of complexing the counter ion of its potassium ‘filling’.. 818. M. Control of Ion Transport Through Lipid Membranes Ulrich J. Pflugrath. W... Shimanouchi..y phosphorus atoms.. Meyer..rsc.org | doi:10. antibody-antigen. M. R.. C. Nikolelis. Bernstein. P.’ A large number of biochemical reactions based on enzymesubstrate . R.then in hydroxylic solvents at neutral pH. Mississauga. The size of cavity required to complex various anions from chloride to ATP was also estimated by using molecular graphics for the bis(crown) designs. J.. J. Dr. A. and Pascard.. T. 1991. Chem. 1985. E. I. 68. Dimitrios P. When ethylenediaminetetraacetic acid was added to the solution in slight excess of that required to complex the calcium .5 The Schori-Grodzinski NMR method8 of determining rates of exchange of quadrupolar nuclei between solvated and complexed environments was applied with limited success. Chem. C.. Acta. Bkouche-Waksman. Canada The perturbation of the structure of artificial lipid membranes can be monitored by electrochemical methods. I.. MoI. and Shporer. F. Shchori. and Subba Rao..1039/AP9912800366 and it has been postulated that the linker between the two crown rings will form a p ~ c k e t It~occurred to us that if the . and offers opportunities for development of chemically selective biosensors. Jr. Chim. l).. 1985. Department of Chemistry.-P. M. 1 Structural formula of bis(crowns) Downloaded by University of Missouri-Columbia on 21 September 2010 Published on 01 January 1991 on http://pubs. P. 62. B. Tompkinson. F. tetraethylenepentamine. J. F. M. University of Toronto. Koetzle. Further evaluation of the modified potential of the assembly for recognition and binding of anionic substrates in the presence of potassium ions is proceeding. as for example formula (I) (Fig. J.View Online 370 ANALYTICAL PROCEEDINGS. SOC. P.. Michael Thompson. V. I. Vida Ghaemmaghami and Krishna M . T. 3048. prior to development of the new materials as anion sensors. F. likewise extended and protonated.

the nature of such a conductive zone is poorly understood. solvent-free planar BLMs and monolayer films were prepared from a lipid mixture (by mass) containing 34% phosphatidylcholine.rsc. and has also been covalently immobilized through the acidic functional group. Two models of ion conduction through BLMs were considered: ‘hopping’ via hydrophilic sites within the hydrophobic zone of BLMs introduced by the hydroxyl moiety of 10. reducing the in-phase signal component by 95% for both types of metal electrode. At concentrations of the acid above 25%. In order to avoid the effects caused by accumulation of ions on one side of such a stabilized membrane. 19% dipalmitoylphosphatidylserine . a pH change from 7 to 8 caused a conductivity change of 25% ).c. for charged species in lipid membranes. 47% cholesterol and variable amounts of 10and 12-hydroxystearic acid (0-50%).’ The electrochemical effects were observed as conductance changes of the membrane. The conductivity was observed to alter drastically at a lipid composition containing a minimum of 25% phosphatidic acid as this component within the membrane was increased. the ion permeability and monolayer compression results did indicate that HSA had a large effect at low concentrations.c. Surface coverage for most experiments was in the range 40-85% as determined by X-ray photoelectron spectroscopy. .org | doi:10. and achieved detection limits in the range 10-100 nmol dm-3. often provided greater surface coverage than if an equivalent 16-carbon phosphatidylcholine had been deposited directly by the reaction of hydroxyl moieties with silane at the metal surface. The adjustment of pH to control the degree of ionization of the phosphatidic acid had a similar effect to the variation of the amount of the acidic phospholipid within the membrane for experiments carried out at fixed pH. the average surface charge was the dominant factor which determined the magnitude of ion conductivity. This indicates that a conductive zone can be opened reversibly by interaction of an analyte at a membrane in the absence of ionchannel proteins. At compositions of acid less than 25%. and determined by replacement of the HSA component with stearic acid. and that artificial ‘ion channels’ had been generated by virtue of the edge activity of HSA.g. phosphatidylcholine) were attached to both the platinum and gold surfaces. mass composition of the charged lipid. number of chains (one or two). where covalent linkages between the support and the lipidreceptor molecules are desirable. and was dependent on the deposition procedure. carboxylic acid and ester. and transport through interfacial regions between phase domains which represent .1039/AP9912800366 ions. areas of low steric density and structural order within monolayers. head group charge and head group size ( e . as exemplified by the initial deposition of aminopropyltriethoxysilane (APTES) onto platinum followed by linkage of a 10-carbon phosphatidylcholine through an amide bond to the amino group of APTES. The electrochemical results indicated that the best blockage of ion conductivity occurred when the amphiphiles contained long hydrocarbon chains. and suggests a general method for evaluation of pK. ion conduction occurred through zones that were enriched in the charged lipid. g . Electrochemistry of Surface-immobilizedMembranes A portable admittance modulation measurement device was constructed. The ion conductivity could be used to measure accurately the pK. with the limit of detection for valinomycin being at the 1 nmol dm-3 concentration level. admittance modulation lipid membrane-based biosensor that operates on the basis of control of ion permeation by artificial ion channels is described. The ion currents were found to increase approximately exponentially with the mole ratio of HSA. Ion conductivity in a small d. the measurements must be made by driving the system with an a. Analogues of natural lipids such as dimyristoylphosphatidylcholine reduced the in-phase component by values of about 50%. Metal electrodes were used as supports for covalent attachment of amphiphiles. Surface attachment of amphiphiles to this metal was achieved by sulphur-gold interaction^. however.^ A wide variety of amphiphiles differing in hydrocarbon chain length. Based on results of studies of cystic fibrosis which implicated hydroxystearic acid (HSA) as a contributing factor in altered biomembrane function. Species such as trichlorooctadecylsilane and octadecylthiol provided the best blockage. Subsequent incubation of lipidcoated electrodes in solutions containing membrane-soluble species such as cholesterol greatly reduced the magnitude of the in-phase component of the signal to values approaching those found for BLMs.or 12-HSA. .~ were prepared by vacuum deposition of a 250 nm layer of the metal onto a 30 nm layer of chromium that covered borosilicate glass slides. value associated with the acidic lipid within a planar BLM. system were tested by studying the interaction of the ionophore valinomycin with planar BLMs. Enzymically active urease has been adsorbed onto these acidic surfaces. Modification of this system to evaluate a biosensing strategy was then carried out. NOVEMBER 1991. In order to elucidate the role of the hydroxyl moieties in ion permeability the transmembrane ion current was corrected for the effect of the negative surface charge of the carboxylic acid.c. Control of Ion Permeability Through Planar Bilayer Lipid Membranes Ion conductivities through solvent-free planar bilayer lipid membranes (BLMs) formed from mixtures of egg phosphatidyl choline and dipalmitoylphosphatidic acid were evaluated to determine the effect of surface charge and phase domain formation on the process of ion translocation. and both systems showed good sensitivity to pH (e. This was attributed to the presence of a phase transition induced by the phosphatidic acid. A further series of analytical experiments were carried out to develop electrodes that were sensitive to pH variations to extend the concept of control of phase domain structure to immobilized membranes. Two-step attachment procedures. The structures of monolayer films at the air-water interface of a Langmuir-Blodgett trough were studied by pressure-area correlations and by further correlations with microscopic phase separation as revealed by fluorescence microscopy. These latter electrodes were tested for response to the presence of valinomycin. VOL 28 371 Downloaded by University of Missouri-Columbia on 21 September 2010 Published on 01 January 1991 on http://pubs. acidic phosphate. Determination of the mechanism of ion permeation and establishment of control of the energetics associated with conductive pathways would permit optimization of the structure of lipid membranes for biosensor development. Further development must include mechanical stabilization of a lipid membrane onto a solid electrode . The results suggested that the physical location of ion permeation through BLMs containing low concentrations of HSA was predominantly at interfacial zones at the edges between domains.1 mol dmP3 KC1 electrolyte) at the membrane-solution interface as predicted from electrical double layer theory. the chain length and the number of chains. chain polarity. The sensitivity and detection limit for the a. While the two mechanisms are not distinct. voltage field was controlled by the surface distribution of potassium ions (0.3 Immobilization of amphiphiles was carried out by reaction of the hydroxyl sites with ~ i l a n eGold electrodes .View Online ANALYTICAL PROCEEDINGS. voltage and by monitoring admittance with a phase-sensitive amplifier.c. Linear 10-carbon silane and thiol carboxylic acids were immobilized onto platinum and gold surfaces. Progress towards a surface-stabilized a. It was found that the conductivity of the membranes could be approximated as a linear function of the per cent. and was designed to measure both the in-phase and out-of-phase signal components for determination of ‘effective’ ion current and membrane capacitance. Platinum electrodes with a surface area of 1 cm2 were oxidized to provide a high density of surface hydroxyl sites. the electrode signal for Ca2+ was eliminated.

1180. which is related to the electric field resulting from the surface dipole layer. ZEEE Electron Devices. M. S.g. optical absorptivity.1039/AP9912800366 Gas Sensors Using the Work Function of Organic Semiconductors Jiii Janata and Jan Langmaier Department of Materials Science and Engineering. Krull. K. C. J. conductance. University of Utah. 2842. . There are two components of the WF: the bulk contribution. This fact has been exploited in the design and development of wellknown potentiometric sensors for hydrogen. USA The key issue in the development of chemical sensors is the design of new chemically selective layers. which is related to the chemical potential of an electron in the phase and represents the affinity of the electron for the matrix. However. Aniline can be easily polymerized from acidic media3 on the Pt plate of the vibrating capacitor and its WF can be measured against a suitable reference plate. in the so-called vacuum reference level. Analyst. References 1 Krull. Downloaded by University of Missouri-Columbia on 21 September 2010 Published on 01 January 1991 on http://pubs. U. U. Measurement of the WF provides information about the electronic properties of a material. For example.rsc.. The latter has been used in this work to develop and characterize a selective layer for hydrogen cyanide based on electrochemically prepared polyaniline (PANI) . Chem.. particularly for the sensing of gases. UT 841 12. The parameters that are modulated by the chemical interactions include mass. and definitive spectroscopic results. stainless steel.g.org | doi:10. G. 1987. 111. Anal. . Kallury. 1985.. J. In WF sensors it is a necessity that at least one interface of the selective layer is capacitively coupled to the remainder of the sensor structure. indicate that this has been accomplished and that sub-micromolar detection levels can be achieved for the substrate with good reversibility and longevity. 2 Sugawara. 1235. although it was proposed as a gas chromatographic detector almost 40 years ago. D.c-- e ~ ' On the other hand when the film is prepared in the oxidized state and/or when the AgCN complex is present the reaction proceeds according to the scheme: [Pt-PANI-Ag-AgCN] + HCN - e- [Pt-PANI-H+ .' This condition is satisfied in a suspended gate field-effect transistor (SGFET)2 and in its macroscopic counterpart the vibrating capacitor. and the surface contribution. Glycerine facilitates proton transfer from the silver clusters to the PANI backbone : [Pt-PANI-Ag] + HCN Slow Fast [Pt-PANI-H+... the asterisk signifies the heterogeneity) its WF decreases on exposure to HCN. In this paper the fundamental aspects of the WF will be reviewed. To date. This paper will be restricted to a discussion of the interactions of organic semiconductors with the gaseous phase and will focus particularly on the chemical modulation of the WF. 369. and Thomas.Ag( CN)2] ? A tilycerine 1 In this instance the HCN molecule dissociates forming a strong Ag(CN)* complex and the proton is again transferred to . The best known device which measures the WF is the vibrating capacitor (Kelvin probe). It is defined as the work that has to be used in order to extract an electron from the interior of a phase and place it outside the reach of image forces. non-linear optics. M. This phenomenon is the basis for a new class of electrochemical sensors. When the PANI*Ag layer is prepared in the reduced state (PANI *Ag is a heterogeneous system. The operating characteristics of solid-state devices based on metal-insulator-semiconductor junctions. they are also being investigated as possible sensor materials in a wide range of applications. 59. such as insulated gate field-effect transistors or metal-insulator-semiconductor diodes. Anal. It plays a key role in the distribution of electrons in solid-state structures.. when the Ag-AgCN system is incorporated in PANI the layer becomes sensitive to HCN. and Umezawa. The WF of PANI itself is not affected by HCN. solvent casting or electrochemical deposition. which use palladium as the gate metal. 4 Ghaemmaghami. superconductors and molecular electronics. The kinetics and the polarity of the change of the WF depend on several factors. 32. its potential for chemical analysis of gases assessed and examples of general solid-state chemical sensors based on its chemical modulation will be given. organic semiconductors prepared by electro-oxidation under different conditions have a different WF. Sanghera. depend directly on the WF of the gate metal. e. Tentative electrochemical results. The response becomes reversible when the electropolymerization is carried out from a glycerine-1 mol dm-3 HZS04 mixture. and in transistors using organic semiconductors which have been shown to respond to a variety of organic vapours. 225. 1986. Galvani potential and work function (WF). Chim.. Organic semiconductors have attracted considerable attention as the materials for such diverse applications as power sources.View Online 372 ANALYTICAL PROCEEDINGS. Not surprisingly. H . which is further affected by the presence of other electron donors/acceptors. e. J.AgCN] T Glycerine 1 . VOL 28 The intent was to use the urease-urea reaction to generate a local transient pH gradient which would perturb the membrane structure.. affects the catalytic properties of solid materials and determines the rate of corrosion and chemical resistance of materials. The electron WF is one of the fundamental material constants.. V. and Thompson. G. Thompson. the WF has been used analytically only rarely. M. Because of its size it is impractical as a sensor.. It is necessary to realize that organic semiconductors can be deposited in different ways.. 1989. 3 Moody. Sazawa. R. by sublimation. Y . K. and Davies. Salt Lake City. NOVEMBER 1991.. The choice of the deposition technique used is determined by the constraints given by the sensor itself. M. We are grateful to the Canadian Defense Research Establishment-Suffield and the Natural Sciences and Engineering Research Council of Canada for financial support of this work. M. Kojima. J. A considerable advantage of this approach is that the film on the working plate can be examined by a variety of auxiliary spectroscopic and microscopic techniques.. Acta...

We have investigated this approach by synthesizing pyrrole substituted in the N-position with a benzo-15-crown-5 derivative. pH measurements were made using the oxidized electrodes with a commercial pH meter and calomel reference electrode. in turn. M.' We have investigated the application of electropolymerized films as a method for producing modified electrode surfaces for use in chemical sensors and biosensors. This leads to the adsorption of cytochrome c at the polymer surface in the correct orientation for electron transfer between the polymer and the haem group . J . Electrochemically polymerized films of phenols can also be used to immobilize glucose oxidase at an electrode surface. Downloaded by University of Missouri-Columbia on 21 September 2010 Published on 01 January 1991 on http://pubs. Electroanal. When the matrix is oxidized (low WF) it can accept electrons and the WF increases. University of Warwick.~ Immobilization of Glucose Oxidase The electropolymerization of pyrrole and N-methylpyrrole from buffered aqueous solutions can be used to immobilize glucose oxidase and other enzymes at electrode surfaces. The films are stable at pH values less than 5 but dissolve slowly in aqueous solution above pH 7. 493. J. Much of this work has concentrated on the use of conducting polymer films formed from substituted pyrroles or other heterocyclic monomers but we have also made use of poly(pheno1ic) films. At pH 7 some portion of the carboxylate groups in the poly(5-carboxyindole) are deprotonated and can be used to hydrogen bond to protonated lysine residues around the haem edge in cytochrome c. 4 Blackwood. The method is well suited to the deposition of films onto microelectrode electrode structures formed by photolithography.6 The immobilized enzyme remains active and glucose can be detected by using electrodes of this type either with oxygen as the mediator or when using an artificial redox mediator such as ferrocenecarboxylic acid. .. Plenum Press. in Chemical Sensor Technology.2 This interaction between the carboxylate groups and the lysine residues mimics the hydrogen bonding interactions which are believed to play an important role in electron transfer between cytochrome c and cytochrome oxidase. In principle. In the resulting enzyme-loaded films the behaviour is determined by the balance of the diffusion of reactants and products within the film and the kinetics for the immobilized enzyme. For polypyrrole and polythiophene this proton transfer reaction is absent and the response to HCN is irreversible. T. In order to understand the behaviour of these films it is necessary to model these processes and to compare the predictions of these models with the experimental r e s ~ l t s . Chem.. we have estimated the kinetics for the oxidation of glucose by the immobilized enzyme. Principles of Chemical Sensors.. The selectivity of this material to a variety of environmentally important gases remains to be tested.. The response is logarithmic in the range 5-50 ppm and has square-root-time dependence. its natural redox partner. D. 95. Analysis of the responses of such Ion-sensitive Polymers Films of poly(5-carboxyindole) can be grown from acetonitrile solutions. the polymer. In each instance the polymer appears to be electro-inactive towards re-oxidation of the mediator. Elsevier. it should be possible to confer ion selectivity on a conducting polymer film by attaching suitable substituents to . J ..org | doi:10.1039/AP9912800366 This work was supported by a contract from BWB and by a grant from the EPA Office of Exploratory Research. Grant NO. N. Applications of Electropolymerized Films in Electrochemical Sensors Philip N. Amsterdam. G . by using these data and data from the kinetic analysis of the response of these films to glucose. Chem. Bartlett Department of Chemistry. R-816491-01-0. and Josowicz.259. 2 Josowicz. and then held at +800 mV versus SCE and the current allowed to decay to zero to convert the film into its oxidized form. 3 Zotti. . References 1 Janata. Fourier transform infrared studies of the polymer films indicate that this loss of conductivity of the film is caused by reactions with hydrogen peroxide generated by the enzyme. Phys. ~ Studies of glucose oxidase immobilized in poly( N-methylpyrrole) films show that when the natural redox partner. indicating predominantly bulk interaction.rsc. The electroneutrality of PANI is maintained by the inflow of electrons from the reference plate which is equivalent to the increase of the WF. The method is simple to carry out and the deposition of the film is readily controlled by control of the electrode potential. S . 235. alters the electrochemistry of the film. When the polymer is transferred into aqueous solution the degree of ionization of these groups varies with the solution pH and this. These were made by the electropolymerization of the monomer from acetonitrile onto 125 pm diameter platinum wires sealed in heatshrink PTFE. VOL 28 373 the PANI backbone. It was found that these kinetics are not significantly different from the values obtained in homogeneous solution. Seiyama. 1988. This result confirms the mechanism of charge transfer between the guest molecule and the m a t r i ~if ~ matrix is reduced (high value of WF) it acts : the as an electron donor and the WF decreases. . The resulting conducting polymer has a carboxylic acid substituent on every monomer unit of the chain. Cattarin. ed. and Janata. This might be advantageous because the mixed ionic and electronic conductivity of the resulting conducting polymer could then be utilized to make small ion-selective sensors. The pH dependency of the electrochemistry of poly(5-carboxyindole) can be used to make small pH-sensitive electrodes. Studies in which oxygen is replaced by ferrocenecarboxylic acid or hexacyanoferrate(rI1) as an artificial mediator species show similar behaviour. 1987. NOVEMBER 1991. The coated electrodes were then transferred into buffered aqueous solution at pH 2 and cycled until a stable response was attained. J. 1991.View Online ANALYTICAL PROCEEDINGS. and the properties of the resulting conducting polymer films have been in~estigated.. oxygen.. and Comisso. M.. Coventry CV4 7AL Electrochemical polymerization is a very convenient technique for the production of modified electrode surfaces.' By using tritium-labelled glucose oxidase we have determined the concentration of enzyme entrapped within our electropolymerized films and. The resulting monomer can be electropolymerized. is used as the mediator species the hydrogen peroxide produced is not oxidized on the polymer but rather must diffuse to the underlying electrode to be detected. New York. 1989.

Chem. References 1 Bartlett. Tebbutt. Further. P. which are not an issue with a disposable device. and a correction is performed by the meter to give the glucose value. The principal criterion for successfully producing or adapting a diagnostic test in disposable form is that a means must be found of constructing a device containing all the necessary components for the test. 1377.2 A poly(viny1 chloride) (PVC) substrate is printed with several layers (Fig. L-Y. G. PVC substrate Conductive silver track Working elec!rode \- .. R.. 1990. 5 Bartlett. It is therefore possible to set up a system whereby ferrocene. Farrington. 911.~ the deacylation of acetaminophen to yield p-aminophenol. which contains all the components of the normal working electrode except for the enzyme. Eastwick-Field. W. 36. N. G. has several improved features including automatic detection of blood application (no button pressing). and re-oxidized at the electrode producing an electrical current dependent on the glucose concentration: two electrodes (working and reference) necessary for the electrochemical reaction. Rhodes and C. Caruana. H. and Moore. this can be interfaced with an electronic meter system which monitors (and may control) the progress of the reaction. Downloaded by University of Missouri-Columbia on 21 September 2010 Published on 01 January 1991 on http://pubs.some of which provide the 0 -@ NHCOCH3 I NH2 I + H20 + CH3COOH (4) OH OH . Its ready availability and toxic effect in overdose make this a substance which is frequently suspected in emergency room admissions. R. J. 359. the usual solution has been to employ one of the large automated analysers to perform the test. 14/15 Eyston Way. 1987/88. the advantages of a singleuse disposable sensor are clear. I thank the following colleagues and students who have contributed to this work: P.. G. J . Actuators.. Most importantly. and Whitaker. In addition. L-Y. D.. VOL 28 electrodes enables the rate constants for the enzyme-catalysed reactions to be estimated and the effect of the substituents on the phenol on the properties of the immobilized enzyme to be investigated... which offers much for improved efficiency and quality of patient care. N. N. 224.Contacts I I I Conductive carbon track Dielectric layer I I Ag-AgCI reference electrode I Fig.. which can be oxidized at an electrode to yield quinoneimine with consequent measurable current: . and Whitaker. avoiding the need to add reagents at the time of use. Acetaminophen Known in the UK as ‘paracetamol’ and in the US as ‘tylenol’.’ Glucose G0Dp-d + GOD. Biosensors. Oxfordshire OX14 ITR For a medical diagnostic product.. A. Tyrrell. G. 261. Chung. Green and Paul 1. A. N. l). the low cost of disposable sensors reduces the fear of expensive damage associated with a re-usable device. D. This type of instrument. This work was supported by the SERC (Grant G R E 67108) and by MediSense. and Whitaker. gluconolactone + GODred + Fe(cp)2+ + GOD. 51. is reduced by GOD in the presence of glucose.. however. temperature com ensation and almost complete freedom from interferences.. J . which is also available in desktop format. V. J. V. 1987. Electroanal. 1 Schematic representation of a disposable glucose sensor strip Glucose Monitoring The basic concept of a biosensor for personal glucose monitoring is simple: reagents and biochemicals necessary for detection are deposited on a disposable sensor device. 4 Bartlett. Whitaker.. Acta. acetaminophen is a widely used analgesic. 1987. P. Electrochim. Any redox-active interferents present in the sample will affect the response of this ‘dummy’ electrode in the same way as the working electrode. + Fe(cp)2 F e ( ~ p + Fe(cp)2f + e)~ - (1) (2) (3) This chemistry is produced commercially in the form of a disposable sensor . P. The detection chemistry which has been most successful in this area is that based on the interaction between glucose oxidase (GOD) and derivatives of ferrocene [bis(cyclopentadienyl)iron] The oxidized forms of ferrocenes (ferricinium ions) are capable of accepting electrons from GOD which has been reduced by the reaction with glucose. N. P.... and Whitaker... Chem. P.rsc. Sens. P.. P. Electroanal. 224.. Chung. with a re-usable sensor there might be concerns with drift and the need for recalibration. has little part to play in the rapidly expanding market of decentralized testing. 2. NOVEMBER 1991. A21-A23. Units 3 & 4. N.’ The last of these has been achieved by the incorporation on the sensor strip of a third electrode. and interprets and displays the results. Z . Benniston.. Benniston. C. J. R. 2 Bartlett. 27. P. A ‘second-generation’ sensor. problems with contamination or carryover are eliminated and sterilization by the user is unnecessary. P. and Farrington. Moore. In an acetaminophen ~ e n s o rthe enzyme aryl acylamidase catalyses . 6 Bartlett. R. Gardner. Dawson. 37. Dawson..1039/AP9912800366 Disposable Single-use Sensors Monika J. Hilditch MediSense Inc. 3 Bartlett. Birkin. Chem. The linearity and accuracy of this system are illustrated in Fig. oxidized at an electrode to form ferricinium. and the whole should be capable of manufacture in large numbers relatively cheaply. 1989.. D. Ali. Abingdon. R.View Online 374 ANALYTICAL PROCEEDINGS.org | doi:10. 3 . and transmit current and potential information to the meter during the measurement. and one of which contains enzyme and mediator in a labile matrix. Where the addition of reagents at the time of the test seems unavoidable. 1991. Electroanal. J . The device should have a stable shelf-life of at least 12 months.

This compound can then be reoxidized at an electrode at the appropriate potential. The principle of the assag is similar to that for acetaminophen: salicylate is converted into catechol by the + 30 33 Theophylline There is a considerable market for sensors capable of monitoring therapeutic drugs present in blood at micromolar concentrations. binding to the enzyme-substrate complex and preventing its further reaction. The parent compound is readily distinguishable electrochemically from the product. and it is this which is measured. and because of the toxicity of salicylate. is prescribed as a bronchodilator in cases of asthma. The line on the graph is the line of identity OH A potential interferent is N-acetylcysteine. For theophylline. 2 Clinical response of the Satellite G glucose sensor compared with a laboratory reference analyser [Yellow Springs Instruments (YSI)]. has been found to be the most satisfactory. Catechol is oxidized to obenzoquinone by the electrode and the current measured. Bacterial Assay System NH A final example of a disposable sensor system is that developed for the detection and measurement of micro-organisms. N-Acetylsalicylate is rapidly converted by hepatic esterases into salicylic acid. Downloaded by University of Missouri-Columbia on 21 September 2010 Published on 01 January 1991 on http://pubs. monitoring of drug concentrations is desirable.View Online ANALYTICAL PROCEEDINGS. in particular that its sensitivity is limited to about lo6cfu ml-' (cfu = colony forming units) by the rate of bacterial respiration. forming a substituted aminophenol which can be reduced at the electrode. the amount of hydroquinone formed in a given time is a measure of the rate of bacterial respiration in the sample and hence of the cell numbers. Aspirin is also used as an anti-inflammatory agent in the management of conditions such as arthritis. and that which is of most interest electrochemically is p-aminophenol phosphate. providing a known amount of enzyme and substrate allows the concentration of inhibitor (theophylline) to be assessed. p-aminophenol. . leaving as options an immunoassay test or some other format such as enzyme inhibition. ~ electrochemical interrogation of bacterial respiration using a mediator compound. The mediator used in the assay is p-benzoquinone. Salicylate N-Acetylsalicylate (aspirin) is another widely used analgesic. VOL 28 Table 1 Design specifications for the bacterial assay system 375 &i + ++ Alternative to 'standard plate count' Capable of producing results rapidly (<1 h) Moderate sensitivity (10s cfu ml-' or better) Economical (<$1per test) enzyme salicylate hydroxylase. Equally. augmenting the current already observed: NH NH2 In order to eliminate this possible interference. the latter approach has been p u r ~ u e d . Linearity of response is obtained by the inclusion of sodium benzoate in the reaction chemistry.. p-benzoquinone. ~ Theophylline. food and environmental applications. which resembles the quinones which occupy a pivotal position in the electron transport chain of bacteria and may compete with these for respiratory electrons. This reagent ensures that the thiol augmentation of response is fully saturated irrespective of the thiol content of the blood.org | doi:10. the sensor strip described includes an absorbent overlay containing glutathione. r Q NH. A disposable sensor for theophylline exploits the interaction of theophylline with the enzyme alkaline phosphatase: the drug behaves as an uncompetitive inhibitor. a member of the xanthine family of compounds. A simple assay of this type has certain limitations. The objectives set out for the system described by Hilditch et ~ 1 are summarized in Table 1. theophylline rapidly becomes toxic and so effective monitoring of concentration is desirable. The approach taken was the . and is monitored in emergency situations for the same reasons as acetaminophen. although the exact site of mediation is unclear. and must be provided in the sensor. The opportunities for this area of testing are almost endless. These substances will usually not be directly detectable in the blood matrix. encompassing clinical. This acts as a pseudo-substrate for the enzyme. on a proph lactic basis. Above its therapeutic range of 55-110 ymol 1. and so the activity of a sample of alkaline phosphatase can be measured by providing p-aminophenol phosphate and measuring electrochemically the amount of p-aminophenol produced. Bacteria respiring in the presence of p-benzoquinone cause it to become reduced to hydroquinone. The cofactor NADH is required by the enzyme. the assay therefore measures viable biomass. NOVEMBER 1991. A wide range of quinones and related compounds have been screened and the simplest. this (and other thiol reagents) can react with the quinoneimine product of the first reactions. which is administered as the antidote for acetaminophen poisoning. which is the therapeutically active form of the drug. effectively modifying its kinetics to give a near-linear response in the clinical concentration range. Alkaline phosphatase will hydrolyse a wide range of substrates.rsc.1039/AP9912800366 0 3 6 9 12 15 18 21 24 27 Mean YSI venous reading/mmol I-' Fig.

W. The meter pumps sample. After loading sample onto the disposable assembly. New York. Charman. The performance of the assay has been validated with a considerable range of aerobic bacterial species.. A.^ They are capable of considerable specificity and sensitivity even when used directly in real samples.. Filter and electrodes are contained in a disposable assembly (Fig.. A . and Williams. 1986. The total assay time is therefore of the order of 15 min.. Carter. 4 . Cranfield Institute of Technology. 4 Response of the bacterial assay system to bacteria (Pseudomonas cepacia) have been obtained with mixed bacterial cultures. P. 1987. Lancet. Wang.. without necessarily incurring the need for complex and expensive instrumentation.. Gibbs. J. yeasts and food and environmental samples. Actu. J . Some conditions. C. Amsterdam.View Online 376 ANALYTICAL PROCEEDINGS.rsc. Holman.. 1237.. D. and Scott. 1991.. Watson. which is maintained at constant temperature. it has been Embossed and textured P V C A typically found to give a linear response with a sensitivity of about lo4 cfu ml-' (Fig. VOL 28 Downloaded by University of Missouri-Columbia on 21 September 2010 Published on 01 January 1991 on http://pubs.6 Indeed. Bedford MK43 OAL Numerous definitions of a biosensor pervade the recent scientific literature. R. Actu. M. F.. E. This paper will review the requirements of several areas where amperometric biosensors are likely to make an impact. Barrett. S. ed. J. and washing with buffer..5 Clinical applications are driven by the need for cost effective patient care. benefit from self-tests usable in the home. Matthews. Turner Biotechnolog y Centre.. F. and Vale.. Application of the technology to other areas such as bacterial monitoring promises to extend further the boundaries of analytical chemistry. Burton. The disposable assembly fits into a housing built into the meter which automatically interfaces with the fluid handling and electrical contacts. R . A few recent or new examples of biosensor technology that are likely to prove a commercial success4 will be illustrated. accuracy and freedom from sample pre-treatment. A. in Proceedings. the assembly is flooded with mediator solution (which also contains carbon source for the bacteria) and is incubated for 10 min. Cranfield. C 2 100 0 CL v) [ r i 0 10 - r = 0. M. Sullivan. 335. Conclusion Single-use biosensor diagnostics are characterized by convenience of use.... Green.. L.In addition to pure cultures. N. Hughes. F. 3) formed from PVC. Coupled with modern microelectronics they form the basis for a new generation of 'sensitive' computers. M.^. results ) loo0 2. B. F. Chim. removing soluble redox interferents.. Steemson. J . D. D. M. Chim. R. S. J. R. wash buffer and mediator solution as appropriate through the disposable assembly. This allows amplification of the response as cells from a relatively large volume of sample are concentrated into a small reaction volume. and Hill. rapidity. D. K. Bown. The system described overcomes these problems by concentrating bacterial cells on a filter in close proximity to the measurement electrodes.. F. Anal. NOVEMBER 1991. McAleer. S. During this time bacterial respiration is converting benzoquinone into hydroquinone. 1989. the lower half has printed electrodes while the upper half has a recess to contain a disc of glass-fibre filter material. .. 3 Disposable sensor element for use in a biosensor bacterial assay system Applications of Amperometric Biosensors Anthony P. Whether this technical route should be pursued or not depends on the relevance of the features offered by biosensors to the problem. Jones.1 Fig. A . S. in the press. Bayliff. S . E. the cells can be washed when on the filter. O.in Advances in Bioreactor Monitoring.1039/AP9912800366 and that redox-active substances in the sample will interfere. Anal. moreover. 224. Braithwaite. R. Biosensors generally provide continuous information about the concentration of a chemical or group of chemical^. J. 57.. M. D. J. Scott. 1. and Green. Foulds. Chem. J. B.. C. Matthews.. 229. S. for example diabetes. 1990. Hilditch. N. 778. P.Faruday Trans. . and Smith.. which is measured for 30 s at the end of the incubation. Analytical instruments can be comprehensive and automated or decentralized and specialized. .. 39. J. European Association for the Study of Diabetes. H.. Brown. References Green. Clinical diagnostics have dominated biosensor development to date and are likely to continue to be the focus for commercial successes over the next five years . a biosensor can be considered as one possible solution to a particular analytical problem. E. S. J.. 793..' Taking a pragmatic view. . 1990. SOC. Academic Press. and Green.. N. Lancet. Frew. M. J. N... C . Artijicial Insulin Delivery Systems Pancreas and Islet Transplantation. A. I.988 1 1 I I I 103 104 105 106 107 108 Se nsit ivit y k f u mI . 1991. 82. . Filter disc c> - with electrodes Fig. Wilshere.org | doi:10.

2393. Alberti.. A.. J . S . 16 Reach. 1991. Amperometric detection of microbial contamination2' of milk has reached the manufacturing prototype sta e in our hands with a detection limit of lo4 organisms ml-' obtained within 20 min in a completely 'hands off' format.. furnishing the ossibility of detecting a wide range of pathogenic organisms. G. Blum. Cranfield. eds. Anal. and Turner. Lab. P. L. 1991.. A. 1990. 1988. A. Diagnostic tests that make sense to perform in the home are few and far between. P. S. 8 (3A). A. Enzyme Microb. F.. D.. P. 1989.. Amperometric biosensors have recently become commercially available for use in situ in fermentation monitoring with broad consequences for the food and biotechnology industries. 1990. 4. 14 Hendry. A . Allen. F. P.. 66.. Advances in Biosensors. . 13 Cardosi. M. but the frequency with which these tests are performed makes an instrumented assay uncompetitive with the elegant visual assays now marketed. P. Bioelectron. ethanol and lactate. 6. creatinine and lactate. Biomaterials. Instrumentation and Processing: The World Biotech Report. J. A m . Appl. 1987. pp. pp. Recent work in our laboratories has shown that screen-printed enzyme electrodes for glucose. M.3. Alberti. quality and compliance with legislation. 2 Turner... F. 17.17A n interesting compromise has recently been announced by an Italian company. 299. P. S. 6. 1991. Sens. Willmer. NOVEMBER 1991... Birch. 24(8). and Alcock.. A. J. London.. Warner. P. and Turner. . Pregnancy testing is an obvious example.. Int. and Turner. 5 . V. S. 9 019 126.. Medicine and food provide the prime focus for new products. Br. R . urea. Biosensors: A New Realism. Biosensors.. Bull. Anal.. using tetrathiafulvalene as mediator.. P. 47-61. J. One interesting new development with particular relevance to this area is the discovery of organic phase enzyme electrodes. pp. respectively. Equally. 254-272. S . 125-137.. Res. P. Bioelectron. 37... Marcel Dekker. for example. 50. C. for example. I. andTurner. G. 16. Biotechnol. F. P. glucose. 19 Rawson. P. A . vol. 18 Brooks. Amsterdam. F.. 4 Turner. 10 Cardosi. Cranfield Biotechnology. Amsterdam. but many smaller companies are searching for niche markets and might furnish some fascinating new gadgets. A.. A.. and Turner. 1991. F. P. New evidence suggests that mediators can be less toxic than feared. 36. Lab. A. 5 Anon.. M. SOC. in The Diabetes Annual. M.. Technical issues concerning the developers include fabrication technologies and a general drive towards miniaturization.. Much of the technology developed for clinical applications will find other uses in industry. Elsevier. J.. K. C. P. Technol. M. 15 Kulys. 3 Turner. Lett. 459... Schneider. 1989. J. 1989. and Turner. and Taylor. P. G. 9. 1991. G. Other promising analytes that are attracting commercial development of pocket-sized devices include total cholesterol. F. Metab. Lett. the LD50 in mice of tetracyan~quinodimethane'~ and tetrathiaf~lvalene~~' recently discovered mediators) is (two 1225 and 710 mg kg-'. 23 Hall. a clear trend within industry critically t o evaluate and invest in focused areas is emerging. A.. W. The printing technology that has been developed for the mass production of one-shot devices might find application in reusable or continuous use devices. Higgins. F. lack of biocompatibility remains a major hurdle to the application of sensors inside the body for critical care or long-term therapeutic purposes. P. Biochem. Stanley. References 1 Turner. E. 137. New York. F. the proposed product consists of a wearable microdialysis system incorporating a non-mediated enzyme electrode for continuous monitoring in diabetics. F. andTurner. Swain. Int. Industry is seeking sensors to improve productivity. L. Chim.. . F. 17 Coughlan. and Turner.... prostatic acid phosphatase (a tumour marker) or estradiol.' can be used over 2000 times. . A key issue in tackling large markets is the requirement for inexpensive and reproducible mass production of the disposable biosensor element. K. A.. in Biosensors. F. andTurner. M.. A. and Wilson. Biosensors: Fundamentals and Applications. G. vol. 1991. 1991. in the press. in Biosensors: Principles and Applications. 1989. Acta. l8 environmental monitoring" and defence. Higgins. simple amperometric devices can be constructed which are capable of highly sensitive immunoassay of analytes such as thyroid stimulating hormone. P.. pp.. Acta.1039/AP9912800366 material.View Online ANALYTICAL PROCEEDINGS.. Johannsson. M. allowing executives to transform themselves into skilled analytical chemists overnight. and Cardosi. J. 234. 20. 1.. F.Y2 A further area of interest is in vivo m ~ n i t o r i n g .. and Coulet.. M. Anal.Trans. F . 11 Bannister. J. Downs. however. 9 D'Costa. J.. G. Actuators. F. S ...rsc. A. Hendry. 1. 1990.22. and Higgins.. 1991. Concern has been expressed. . vol. 1988. A. G. and Turner. Once investment has been made in such a production facility it is desirable to find further applications for the technology. P. Oxford. H.. for example.. J. 87. 1991. 1(3). L. . L. F. Put. 8 Turner. J. Biosens. F. 21 Saini. Mediated '~ amperometric enzyme electrodes offer advantages over oxygen-consuming systems in their relative independence from variations in oxygen tension. . D. 6 Cardosi. Oxford University Press. A.. and compliance with legislation. P. P. 20 Turner. F. A. P. London.. I. P. vol. 1991. A.. B. Newman. about the toxicity of the mediators used. Online. P... M.19. 7 Palleschi. and Coulet.lS While many promising sensors have been described. A.'**" Some speculative work is underway to perform electrochemical detection of DNA hybridization. VOL 28 377 the world's most successful biosensor is a pen-shaped blood glucose monitor which addresses this market.. A.. M. A. 249. Biosens. F. 25. E.. 433. F.org | doi:10.. S. M. 6. P. F.. S.21722These instruments are capable of operating in oils or fats23 and can also offer improved performance in aqueous samples by. and Turner. P. Biodeterior. 28. J. Thevenot. 12 Downs. I. Fothergill... 271-301. 1989. F. A. F. Karube.. and Krall.. J. in the press. This has been achieved by using proprietary membrane technology acting as a reservoir of the mediator. JAI Press. Horm. I. P. M. Biotechnol. 22 Saini. 7. F. Anal. P. Environmental applications of biosensors are characterized by a desire to protect workers and the public from toxic Downloaded by University of Missouri-Columbia on 21 September 2010 Published on 01 January 1991 on http://pubs. S . and Turner. Hall. M. Elsevier. in The Diabetes Annual.. E. and Krall..' Such elements might be useful in larger machines where the throughput permitted by biosensors can out-perform conventional systems or where a competitive advantage can be achieved by broadening the spectrum of analyses offered to include. 1990. automatically concentrating contaminants present in drinking water. A. Chim. F. eds. As the academic literature on biosensors continues to diversify. in the press. 1989. eds..

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