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`Handbook of Chemical and
`Biological Sensors
`
`Edited by
`
`Richard F Taylor
`
`Arthur D Little Inc.
`
`Jerome S Schultz
`
`University of Pittsburgh
`
`Institute of Physics Publishing
`Bristol and Philadelphia
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`© IOP Publishing Ltd 1996
`
`All rights reserved. No part of this publication may be reproduced, stored
`in a retrieval system or transmitted in any form or by any means, electronic,
`mechanical, photocopying, recording or otherwise, without the prior permission
`of the publisher. Multiple copying is permitted in accordance with the terms
`of licences issued by the Copyright Licensing Agency under the terms of its
`agreement with the Committee of Vice-Chancellors and Principals.
`
`British Library Cataloguing-in-Publication Data
`
`A catalogue record for this book is available from the British Library.
`
`ISBN O 7503 0323 9
`
`Library of Congress Cataloging-in-Publication Data are available
`
`IOP Publishing Ltd and the authors have attempted to trace the copyright holders
`of all the material reproduced in this publication and apologize to copyright
`holders if permission to publish in this form has not been obtained.
`
`Published by Institute of Physics Publishing, wholly owned by The Institute of
`Physics, London
`Institute of Physics Publishing, Techno House, Redcliffe Way, Bristol BS 1 6NX,
`UK
`US Editorial Office: Institute of Physics Publishing, The Public Ledger Building,
`Suite 1035, 150 South Independence Mall West, Philadelphia, PA 19106, USA
`
`Typeset in TEX using the IOP Bookmaker Macros
`Printed in the UK by J W Arrowsmith Ltd, .Bristol
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`Contents
`
`Preface
`
`Introduction to chemical and biological sensors
`Jerome S Schultz and Richard F Taylor
`
`1.1
`
`Introduction
`References
`
`Section I. Basics of Sensor Technologies
`
`2
`
`Physical sensors
`Robert A Peura and Stevan Kun
`
`2.1 Piezoelectric sensors
`2.2 Resistive sensors
`2.3
`Inductive sensors
`2.4 Capacitive sensors
`2.5 Bridge circuits
`2.6 Displacement measurements
`2.7 Blood pressure measurements
`References
`
`3
`
`Integrated circuit manufacturing techniques applied to
`microfabrication
`Marc Madou and Hyunok Lynn Kim
`
`Introduction
`3.1
`3.2 Photolithography
`3.3 Subtractive techniques
`3.4 Additive techniques
`3.5 Comparison of micromachining tools
`Acknowledgment
`References
`
`xi
`
`1
`
`I
`8
`
`11
`
`12
`16
`24
`28
`33
`36
`36
`42
`
`4S
`
`45
`45
`57
`67
`79
`81
`81
`
`V
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`vi
`
`4
`
`s
`
`CONTENTS
`
`Photometric transduction
`Donald G Buerk
`4.1
`Introduction
`4.2 Phototransduction based on interactions between light and
`matter
`4.3 Applications for photometric transducers
`4.4 Concluding remarks
`References
`
`Electrochemical transduction
`Joseph Wang
`5.1
`Introduction
`5.2 Amperometric transduction
`5.3 Potentiometric transduction
`5.4 Conductimetric transduction
`5.5 Conclusions
`References
`
`6 Modification of sensor surfaces
`P N Bartlett
`6.1
`Introduction
`6.2 Covalent modification of surfaces
`6.3 Self-assembled monolayers and adsorption
`6.4 Polymer-coated surfaces
`6.5 Electrochemically generated films
`6.6 Other surface modifications
`6.7 Conclusions
`References
`
`7
`
`8
`
`Biological and chemical components for sensors
`Jerome S Schultz
`7.1
`Introduction
`7.2 Sources of biological recognition elements
`7.3 Design considerations for use of recognition elements in
`biosensors
`References
`
`Immobilization methods
`Richard F Taylor
`8.1
`Introduction
`8.2
`Immobilization technology
`8.3
`Immobilization of cells or tissues
`8.4 Conclusions
`References
`
`83
`
`83
`
`90
`104
`118
`119
`
`123
`
`123
`123
`130
`135
`136
`136
`
`139
`
`139
`140
`148
`154
`157
`161
`164
`164
`
`171
`
`171
`172
`
`188
`200
`
`203
`
`203
`203
`212
`214
`215
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`CONTENTS
`
`BIiayer lipid membranes and other lipid-based methods
`Dim/trios P Nikolelis, Ulrich J Krull, Angelica L Ottova and H 1i
`1lc,1
`9.1
`9.2
`9.3
`9.4
`9.5
`
`Introduction
`Experimental bilayer lipid membranes
`Electrostatic properties of lipid membranes
`Electrochemical sensors based on bilayer lipid membranes
`Summary/trends
`Acknowledgments
`References
`
`Dlomolecular electronics
`Felix T Hong
`I 0.1
`Introduction
`I 0.2 Advantages of using molecular and biomolecular materials
`I 0.3 Electrical behavior of molecular optoelectronic devices: the
`role of chemistry in signal generation
`I 0.4 The physiological role of the ac photoelectric signal: the
`reverse engineering visual sensory transduction process
`I 0.5 Bacteriorhodopsin as an advanced bioelectronic material: a
`bifunctional sensor
`10.6 Bioelectronic interfaces
`10.7 Immobilization of protein: the importance of membrane
`fluidity
`I 0.8 The concept of intelligent materials
`10.9 Concluding summary and future perspective
`Acknowledgments
`References
`
`Sensor and sensor array calibration
`W Patrick Carey and Bruce R Kowalski
`11.1 Introduction
`11.2 Zero-order sensor calibration (individual sensors)
`11.3 First-order sensors (sensor arrays)
`11.4 Second-order calibration
`11.5 Conclusion
`References
`
`Mkrofluldics
`Jay N Zemel and Rogerio Furlan
`I 2. I Introduction
`I 2.2 Fabrication of small structures
`I 2.3 Sensors for use in microchannels
`
`vii
`
`221
`
`221
`224
`235
`240
`253
`253
`254
`
`257
`
`257
`258
`
`259
`
`268
`
`271
`274
`
`276
`280
`281
`282
`282
`
`287
`
`287
`289
`294
`308
`313
`313
`
`317
`
`317
`322
`326
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`12.4 Flow actuation and control
`12.5 Fluid flow phenomena
`12.6 Conclusion
`References
`
`Section II. Examples of Sensor Systems
`
`13 Practical examples of polymer-based chemical sensors
`Michael J nerney
`13.1 Introduction
`13.2 Roles of polymers in chemical, gas, and biosensors
`13.3 Property/function-based selection of polymers for sensors
`13.4 Polymer membrane deposition techniques
`13.5 Example: polymers in fast-response gas sensors
`References
`
`14
`
`Solid state, resistive gas sensors
`Barbara Hofjheins
`14.1 Introduction
`14.2 Materials
`14.3 Enhancing selectivity
`14.4 Fabrication
`14.5 Specific sensor examples
`References
`
`15 Optical sensors for biomedical applications
`Gerald G Vurek
`15.1 Why blood gas monitoring?
`15.2 Oximetry
`15.3 Intra-arterial blood gas sensors
`15.4 Sensor attributes affecting performance
`15.5 Accuracy compared to what?
`15.6 Tools for sensor development
`15.7 Examples of sensor fabrication techniques
`15.8 In vivo issues
`15.9 Summary
`References
`
`16 Electrochemical sensors: microfabrication techniques
`Chung-Chiun Liu
`16.1 General design approaches for microfabricated
`electrochemical sensors
`16.2 Metallization processes in the microfabrication of
`electrochemical sensors
`
`333
`334
`341
`343
`
`349
`
`349
`349
`355
`359
`360
`368
`
`371
`
`371
`371
`378
`382
`386
`394
`
`399
`
`400
`401
`406
`406
`413
`413
`414
`414
`416
`416
`
`419
`
`420
`
`423
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`CONTENTS
`
`16.3 Packaging
`16.4 Practical applications
`16.5 Examples
`References
`
`17 Electrochemical sensors: enzyme electrodes and field effect
`transistors
`Dorothea Pfeiffer, Florian Schubert, Ulla Wollenberger and
`Frieder W Scheller
`17.1 Overview of design and function
`17.2 Description of development steps
`17.3 Transfer to manufacturing and production
`17.4 Practical use and performance
`References
`
`18 Electrochemical sensors: capacitance
`TM Fare, JC Silvia, J L Schwartz, MD Cabelli, CDT Dahlin,
`S M Dallas, C L Kichula, V Narayanswamy, P H Thompson and
`L J Van Houten
`
`18. l Introduction
`18.2 Contributions to conductance and capacitance in device
`response
`18.3 Mechanisms of sensor response: kinetics, equilibrium, and
`mass transport
`18.4 Practical example: fabrication and testing of SmartSense™
`immunosensors
`18.5 Conclusion
`References
`
`19 Piezoelectric and surface acoustic wave sensors
`Ahmad A Suleiman and George G Guilbault
`
`19.1 Introduction
`19.2 Fundamentals
`19.3 Commercial devices
`19.4 Emerging technology
`19.5 Conclusion
`References
`
`20 Thermistor-based biosensors
`Bengt Danielsson and Bo Mattiasson
`
`20.1 Introduction
`20.2 Instrumentation
`
`ix
`
`427
`430
`430
`433
`
`435
`
`435
`436
`450
`451
`454
`
`459
`
`459
`
`463
`
`467
`
`472
`479
`480
`
`483
`
`483
`484
`489
`490
`491
`493
`
`49S
`
`495
`496
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`.JI.
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`CONTENTS
`
`20.3 Applications
`Acknowledgments
`References
`
`496
`510
`511
`
`21 On-line and flow injection analysis: physical and chemical
`sensors
`Gil E Pacey
`515
`21.1 Definitions and descriptions of on-line and flow injection
`21.2 Selectivity enhancements, matrix modification and conversion 520
`21.3 Sensor cell design in FIA
`523
`21.4 Measurements
`526
`21.5 Conclusion
`530
`References
`530
`
`SIS
`
`22 Flow injection analysis in combination with biosensors
`Bo Mattiasson and Bengt Danie/sson
`22. l Introduction
`22.2 Flow injection analysis
`Acknowledgments
`References
`
`23 Chemical and biological sensors: markets and
`commercialization
`Richard F Taylor
`23. l Introduction
`23.2 Development and commercialization
`23.3 Current and future applications
`23.4 Current and future markets
`23.5 Development and commercialization of a chemical sensor or
`biosensor
`23.6 Conclusion
`References
`
`Index
`
`533
`
`533
`534
`548
`549
`
`553
`
`553
`555
`559
`567
`
`570
`577
`577
`
`581
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`Preface
`
`Measurement represents one of the oldest methods used by man to better
`understand and control his life and his world. Since antiquity, new methods
`have evolved and replaced old to allow better, faster and more accurate
`measurements of materials, both chemical and biological. The driving force
`in the evolution of measurement methods is to gain and apply information in
`real time. Characteristics such as specificity, sensitivity, speed and cost all
`contribute to the success or failure of a new measurement technology.
`the evolved products of many
`Chemical and biological sensors are
`measurement systems and many different technologies. Based on physical
`transduction methods and drawing on diverse disciplines such as polymer
`chemistry, physics, electronics and molecular biology, chemical and biological
`sensors represent multidisciplinary hybrid products of the physical, chemical
`and biological sciences. As a result, chemical and biological sensors are able
`to recognize a specific molecular species or event, converting this recognition
`event into an electrical signal or some other useful output.
`The 1980s witnessed the evolution of early chemical and biological sensors
`into more sophisticated and complex. measurement devices. The first electrode(cid:173)
`based sensors were improved and became commercially viable products while
`new chemical sensors and biosensors based on direct binding interactions were
`reduced to practical prototypes and first-generation products. Now, in the 1990s,
`both types of sensors are being improved to new performance levels. By the
`turn of the century, chemical and biological sensors will be used routinely for
`medical, food, chemical and environmental applications and will, themselves, be
`the evolutionary precursors to more advanced microsensors and biocomputing
`devices.
`The diversity of chemical and biological sensors in both type and application
`appeals to a broad group of scientists and engineers with interests ranging from
`basic sensor research and development to the application of sensors in the field
`and on processing lines. To date, no tex.t has attempted to address the needs of
`this broad audience.
`The Handbook of Chemical and Biological Sensors is aimed at all scientists
`and engineers who are interested in or are developing these sensors. The scope
`of the book includes both chemical and biological sensors, as well as the basic
`
`x.i
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`xii
`
`PREFACE
`
`technologies associated with physical sensors which fonn the basis for them.
`The text is divided into two major parts, the first dealing with basic sensor
`technologies and the second with sensor applications. This approach allows the
`reader to first review the scientific basis for sensor transducers, surfaces, and
`signal output; these basic technologies are then extended to actual. functional
`sensors, many of them commercial products. The Handbook, then, is intended
`to be both a teaching and a reference tool for those interested in developing and
`using chemical and biological sensors.
`It is our hope that the Handbook will be useful both to those who are new to
`the sensor area and to experienced sensor scientists and engineers who wish to
`broaden their knowledge of the wide-ranging sensor field. It is our purpose to
`present the many disciplines required for sensor development to this audience
`and to illustrate the current sensor state of the art. Finally. this text addresses the
`hard realities of sensor commercialization since the practical use and application
`of chemical and biological sensors is key to driving their further evolution. It
`is further hoped that this text, and projected updated editions, will become a
`standard reference text for those working with chemical and biological sensors.
`
`Richard F Taylor
`Jerome S Schultz
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`SECTION 1
`Introduction to
`Chemical and Biological Sensors
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`1
`
`Introduction to chemical and biological sensors
`
`Jerome S Schultz and Richard F Taylor
`
`1.1
`
`INTRODUCTION
`
`the era of information:
`is being heralded as
`The coming 21st century
`expanding capabilities for computer-assisted management of information,
`increased capabilities in decision making and process control, and automated
`health care will all add to the pace and quality of life in this new era.
`Our new abilities to simultaneously handle multiple information sources as
`well as vastly more efficient methods for classifying, sorting, and retrieving
`information will put increasing demands on the technologies and instruments
`used for obtaining information in a timely and continuous manner. Today, this
`capability is exemplified by physical sensing and measurement systems, i.e.,
`systems able to detect and measure parameters such as temperature, pressure,
`electric charge, viscosity, and light intensity (see chapter 2 of this text).
`During the 1980s and now the 1990s, it has become apparent that more
`sophisticated measurement devices are necessary to collect the information
`which can be processed in new management systems. Chemical and biological
`sensors have emerged as the means to this end. The basic technologies begun
`in the 1980s and being developed in the 1990s will result in chemical and
`biological sensors with near-infinite capabilities for analyte detection. This new
`generation of sensors will, by the end of this century, become an integral part
`of collection and control systems in nearly every industry and marketplace.
`
`1.1.1 Definition of chemical and biological sensors
`
`Chemical and biological sensors (the latter are also called biosensors) are
`more complex extensions of physical sensors. In many cases, the transducer
`technologies developed and commercialized for physical sensors are the basis for
`chemical sensors and biosensors. As used throughout this text, chemical sensors
`and biosensors are defined as measurement devices which utilize chemical
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`2
`
`INTRODUCTION TO CHEMICAL AND BIOLOGICAL SENSORS
`
`or biological reactions to detect and quantify a specific analyte or event.
`Such sensors differ, therefore, from physical sensors which measure physical
`parameters.
`The distinction between chemical sensors and biosensors is more complex.
`Many authors attempt to define a sensor based on the nature of the analyte
`detected. This approach can be misleading since nearly all analytes measured
`by a chemical or biosensor are chemicals or biochemicals, the exception being
`sensors which detect whole cells. Other authors attempt to define a chemical
`of biosensor by the nature of the reaction which leads to the detection event.
`Again, this is confusing since all reactions at chemical and biosensor surfaces
`are chemical (or biochemical) reactions.
`In
`this text, we distinguish between chemical sensors and biosensors
`according to the nature of their reactive surface. By this definition, chemical
`sensors utilize specific polymeric membranes, either per se or containing
`doping agents, or are coated with non-biological (usually low-molecular-weight)
`materials. These polymeric layers or specific chemicals, attached to the layers
`or directly to the transducer, interact with and measure the analyte of interest.
`The nature of the analyte or the reaction which takes place is not limited with
`such chemical sensors.
`We define biosensors in this text as sensors which contain a biomolecule
`(such as an enzyme, antibody, or receptor) or a cell as the active detection
`component. Again, the nature of the analyte and the reaction which leads to
`detection are not limited in this definition.
`Given these definitions, we can further define the basic components of a
`chemical sensor or biosensor. These include the active surface, the transducer,
`and the electronics/software as shown in figure 1.1.
`The active surface of a chemical or biosensor contains the detection
`component as described above, e.g., a polymeric layer or an immobilized
`biomolecule. Examples of these layers are given throughout this text (e.g., see
`chapters 7-10). It is the interaction between the active layer and the analyte(s)
`being measured that is detected by the transducer. Examples of transducers
`are described in table 1.1 and in chapters 3-6 of this text. The change in the
`transducer due to the active surface event is expressed as a specific signal which
`may include changes in impedance, voltage, light intensity, reflectance, weight,
`color, or temperature. This signal is then detected, amplified, and processed by
`the electronics/software module (see chapter 12).
`An example of a sensor utilizing these three components is illustrated
`in figure 1.2, which shows a schematic of a typical enzyme electrode for
`the detection of glucose (also see chapter 17 of this text). The bioactive
`surface consists of immobilized glucose oxidase (GOD) sandwiched between
`a polycarbonate and cellulose acetate membrane. The transducer is a platinum
`electrode and the electronics are those typically found in any polarograph, i.e.
`an electronic system to measure low currents (on the order of microamperes)
`at a fixed voltage bias on the platinum electrode. The action of glucose
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`INTRODUCI10N
`
`3
`
`Effector
`
`Active Surface
`
`Transducer
`
`• Polymer
`• Enzyme
`• AnlibOdy
`• Aeceplor
`Ere.
`
`• Potenriometnc
`• Amperomerric
`• Optical
`• Thermisror
`• Transistor
`• Piezoelectric
`• SAW
`
`AmpllflcationlStorageJProcessing
`
`Control
`
`Figure 1.1 Basic components of a sensor.
`
`oxidase on glucose results in oxygen depletion, resulting in a depression of the
`oxygen concentration in the immediate vicinity of the polarographic electrode
`transducer. The resulting reduction in steady state current is detected and
`translated to a millivolt output. This output (i.e. reduced availability of oxygen)
`can then be related to increases in glucose concentration.
`While enzyme electrodes represent a successful commercial application of
`sensor technology, their dependence on enzymatic activity sets them apart from
`most other sensors. The majority of chemical sensors and biosensors function
`by binding the analyte(s) to the active surface. Such binding results in a change
`in the transducer output voltage, impedance, light scattering, etc. These types
`of affinity or binding sensors are discussed in chapters 14, 15, 18, and 19 of this
`text.
`
`1.1.2 Historical perspective of chemical and biological sensors
`
`Chemical sensors and biosensors are relatively new measurement devices. Up
`until approximately 30 years ago, the glass pH electrode could be considered
`the only portable chemical sensor sufficiently reliable for measuring a chemical
`parameter. Even this sensor, which has been under continuous development
`since it invention in 1922 (table 1.2), needs to be recalibrated on a daily basis
`and is limited to measurements in solutions or on wet surfaces.
`Other sensing technologies based on oxidation-reduction reactions at
`electrodes were extensively pursued in the 1940s and 1950s providing analytical
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`4
`
`INTRODUCTION TO CHEMICAL AND BIOLOGICAL SENSORS
`
`Table 1.1 Major sensor transducer technologies.
`
`Technology/example
`
`Output change
`
`Examples•
`
`Electronic
`Amperometric
`
`Applied current
`
`Potentiometric
`
`Voltage
`
`Capacitance/impedance
`
`Impedance
`
`Photometric
`Light absorption or scat(cid:173)
`tering; refractive index
`
`Fluorescence of lumines(cid:173)
`cence activation, quench(cid:173)
`ing or polarization
`
`AcousticaVmechanical
`Acoustical
`
`Mass, density
`Calorimetric
`Thermistor
`
`Light intensity, color, or
`emission
`
`Fluorescence or chemilu(cid:173)
`minescence
`
`Amplitude, phase or fre(cid:173)
`quency (acoustic wave)
`Weight
`
`Temperature
`
`Polymer enzyme, anti(cid:173)
`body,
`and whole-cell
`electrodes
`Polymeric and enzyme
`electrodes, FETs, EN(cid:173)
`FETs
`Conductimeters, interdig(cid:173)
`itated electrode capaci(cid:173)
`tors
`
`Ellipsometry, internal re(cid:173)
`flectometry,
`laser light
`scattering
`Surface plasmon reso(cid:173)
`nance, fiber optic wave
`guides, fluorescence po(cid:173)
`larization
`
`SAW devices
`
`Piezoelectric devices
`
`immuno(cid:173)
`Enzyme and
`enzyme reactors
`
`• Abbreviations: FET, field effect transistor, ENFET, enzyme FET; SAW, surface
`acoustic wave.
`
`methods for the detection of metallic ions and some organic compounds. The
`first application of these electrochemical techniques to make a sensor was for
`the measurement of oxygen content in tissues and physiological fluids [4]. Ion
`selective electrodes have provided new measurement capabilities but face the
`same limitations as well as less selectivity than the pH electrode.
`In spite of this limitation, ion selective electrodes have provided some
`of the first transducers for chemical sensors and biosensors (see chapters 13
`and 17 of this text). For example, many chemical sensors use a selective
`membrane containing a specific capture molecule (or dopant) to provide a
`selective permeability for the ion the electrode detects. Thus, a K+ electrode
`::an use valinomycin as its capture molecule as illustrated in figure 1.3 [21].
`These types of chemical sensor provide a basis for the development of a wide
`·ange of sensors based on specific capture molecules.
`The key concept for the adaptation of these electroanalytical techniques was
`:::lark's idea of encapsulating the electrodes and supporting chemical components
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`INTRODUCTION
`
`5
`
`React ion
`2
`
`Reaction
`1
`
`Cellulose
`acetate
`membrane
`
`Polycarbonate
`membrane
`
`0-r ing
`
`Figure 1.2 The basic components of a commercial enzyme electrode (reprinted with
`permission of YSI, Inc.).
`
`by a semipermeable membrane. This allows the analyte to diffuse freely within
`the sensor without the loss of critical components, e.g. the enzyme [4] . The
`concept of interposing membrane layers between the solution and the electrode
`also provided the basis for the first biosensor, a glucose biosensor invented
`by Clark and Lyons [6] and its commercial product illustrated in figure 1.2.
`The first glucose sensor was the precursor to the development of other glucose
`sensors based on a wide range of transduction technologies and utilizing glucose
`oxidase as the active surface detection component. It is notable from figure 1.4
`(22] that a sensor can be developed based on the measurement of any of the
`reactants or products of the glucose/GOD reaction.
`The invention of enzyme electrodes, new transduction technologies, and new
`means to immobilize polymers and biomolecules onto transducers has led to the
`rapid evolution of chemical sensor and biosensor technology during the 1970s
`and 1980s (table 1.2). Examples of these technologies are found throughout
`this text and the reduction of these technologies to practical sensors is found in
`chapters 13-22. Sensor technology is being further advanced by new discoveries
`in conductive polymers, enzyme modification, and development of organic and
`biological components for organic computing devices (chapters 11 and 23).
`These advances will result in the commercialization of a variety of chemical
`and biosensors by the first years of the next century.
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`

`

`6
`
`INTRODUCTION TO CHEMICAL AND BIOLOGICAL SENSORS
`
`Table 1.2 Historical landmarks in the development of chemical sensors and biosensors.
`
`Date
`
`1916
`
`1922
`1925
`1954
`
`1962
`
`1964
`
`1969
`
`1972-74
`
`1975
`
`1975-76
`
`1979
`1980
`1982
`1983
`
`1986
`
`1987
`
`Event
`
`Reference
`
`First report on the immobilization of proteins: adsorption
`of invertase to activated charcoal
`First glass pH electrode
`
`First blood pH electrode
`
`Invention of the oxygen electrode
`
`Invention of the pC02 electrode
`First amperometric biosensor:
`enzyme electrode for glucose
`
`glucose oxidase-based
`
`Method for generating lipid bilayer membranes
`
`Coated piezoelectric quartz crystals as sensors for water,
`hydrocarbons, polar molecules, and hydrogen sulfide
`
`First potentiometric biosensor: acrylamide-immobilized
`urease on an ammonia electrode to detect urea
`First commercial enzyme electrode (for glucose) and
`glucose analyzer using the electrode (Yellow Springs
`Instruments)
`immobilized Acetobac-
`First microbe-based biosensor:
`ter.xylinium in cellulose on an oxygen electrode for ethanol
`
`First binding-protein biosensor: immobilized concanavalin
`A in a polyvinyl chloride membrane on a platinum wire
`electrode to measure yeast mannan
`
`Invention of the pC02/p02 optrode
`First immunosensors: ovalbumin on a platinum wire
`electrode for ovalbumin antibody; antibody to human
`immunoglobulin G (hlgG) in an acetylcellulose membrane
`on a platinum electrode for hlgG measurements
`
`Surface acoustic wave sensors for gases
`
`Fiber optic pH sensor for in vivo blood gases
`
`Fiber-optic-based biosensor for glucose
`
`Molecular level fabrication techniques and theory for
`molecular level electronic devices
`First tissue-based biosensor: antennules from blue crabs
`mounted in a chamber with a platinum electrode to detect
`amino acids
`First receptor-based biosensor: acetylcholine receptor on a
`capacitance transducer for cholinergics
`
`Electrically conductive redox enzymes
`
`[1]
`
`[2]
`
`[3]
`
`[4]
`
`[SJ
`[ 6]
`
`(71
`
`[8]
`
`[9]
`
`[10]
`
`[ 11 J
`
`(12]
`[I I, 13]
`
`(14]
`[ 17]
`[ 15 J
`(16]
`
`(18]
`
`[19)
`
`[20)
`
`Dexcom Inc. v. WaveForm Technologies, Inc.
`IPR2017-01051
`Exhibit 1024
`
`

`

`INTRODUCTION
`
`7
`
`QC
`@O
`
`.N
`
`--- H-bond
`
`a
`
`b
`
`Figure 1.3 Structure of (a) free valinomycin and (b) its complex with K+. Note
`the cooperation of the inner oxygen atoms P, M, and R in the complexation process.
`(Reprinted from (11) with permission of Cambridge University Press.)
`
`1.1.3 The purpose of this handbook
`
`The multiplicity of methods which have been applied to development of glucose
`sensors shown in figure 1.4 illustrates a major problem with chemical sensor
`and biosensor development. During the past two decades, as the need for
`these sensors has emerged, there has been more effort spent on the repeated
`demonstration of chemical sensor and biosensor designs than on focused efforts
`to bring sensors through mass production to commercialization.
`This handbook is designed to address the needs of both development and
`commercialization in one text. The first 12 chapters focus on basic technology
`and methods for developing sensors. These include preparation of the active
`surface, the different types of transducer available for sensors and signal output
`and processing. These aim of these chapters is to provide a knowledge of the
`basic technologies and methods used in sensor development.
`Chapters 13-22 deal with specific examples of sensors and their practical
`reduction to practice. The sensors addressed in these chapters are still mainly in
`the advanced prototype stage, still requiring final transfer to mass manufacturing.
`These sensors represent, however, the initial technologies and products which
`
`Dexcom Inc. v. WaveForm Technologies, Inc.
`IPR2017-01051
`Exhibit 1024
`
`

`

`8
`
`INTRODUCTION TO CHEMICAL AND BIOLOGICAL SENSORS
`
`Determination of glucose in body fluids:
`detection principles employed in biosensors for potentil intl'Clcorporal use
`~ SELECTION
`I
`a-glucose - Oz + H20
`I
`I
`
`gluco&e aidou
`11ciich11m.tr7
`
`D-gluconic acid • 7 kcal
`
`• Hz f 2 •
`I
`I
`
`I
`
`I
`
`coated wire
`(glc - selective
`membrane)
`POTENTIOMETRIC
`
`TRANSDUCTION
`I
`cathodic redu c t ion
`al polarog raphic
`enzyme electrode
`bl electron med io ted
`sensor
`c I metal- catalytic sensor
`AMPEROMETRIC
`
`anodic
`oxidation
`H202 el ec trade
`
`--
`
`THERMISTOR
`
`CALO RI METRIC
`
`a near-infrared
`spectroscopy
`b micro-polarimetry
`c fluorescence
`affinity sensor
`OPTICAL
`
`fluorescence
`quenching
`
`oxidation
`pH
`by KJ
`electrod1
`iodide
`electrode
`f'TsFEf'l
`POTENTIO METJm
`
`Figure 1.4 Determination of glucose in body fluids: detection principles employed in
`biosensors for potential intracorporal use.
`
`will be launched into the 21st century.
`The last chapter in this text deals with sensor commercialization and markets.
`Chemical and biosensors are following a commercialization pathway similar
`to other detection and measurement devices such as analytical chemistry
`instrumentation in the 1950s and 1960s, and immunoassay in the 1970s and
`1980s. Common to these products, sensors will achieve a critical mass which
`will push them into large-scale commercialization by the first part of the 21st
`century.
`
`REFERENCES
`
`[I) Nelson J Mand Griffin E G 1916 Adsorption of invertase J. Am. Chem. Soc. 38
`1109-15
`[2] Hughes W S 1922 The potential difference between glass and electrolytes in
`contact with water J. Am. Chem. Soc. 44 2860-6
`[3] Kerridge PT 1925 The use of the glass electrode in biochemistry Biochem. J. 19
`611-7
`[4) Clark L C Jr 1956 Monitor and control of blood tissue 0 2 tensions Trans. Am.
`Soc. Artif. Intern. Organs 2 41-8
`[5] Stow R W and Randall B F I 954 Electrical measurement of the pC02 of blood
`Abstract Am. J. Physiol. 179 678
`[6] Clark LC Jr and Lyons C 1962 Electrode system for continuous monitoring in
`cardiovascular surgery Ann. NY Acad. Sci. 148 133-53
`
`Dexcom Inc. v. WaveForm Technologies, Inc.
`IPR2017-01051
`Exhibit 1024
`
`

`

`REFERENCES
`
`9
`
`[7] Mueller P, Rudin D 0, Tien HT and Wescott W 1962 Reconstruction of excitable
`cell membrane structure in vitro Circulation 26 1167-71
`[8] King W H Jr 1964 Piezoelectric sorption detector Anal. Chem. 36 1735-9
`[9] Guilbault G and Montalvo J 1969 A urea specific enzyme electrode J. Am. Chem.
`Soc. 91 2164-5
`[ 10) Davies C 1975 Ethanol oxidation by an Acetobacter xylinium microbial electrode
`Ann. Microbiol. A 126 175-86
`Janata J 1975 An immunoelectrode J. Am. Chem. Soc. 97 2914-6
`[11)
`[12) Lubbers D Wand Opitz N 1975 Die pC02/p02-0ptrode: Eine neue pCOi-bzw.
`p02-Messonde zur Messung des pC02 oder p02 von Gasen und Flilssigkeiten
`Z. Naturf. c 30 532-3
`[13) Aizawa M, Morioka A, Matsuoka H, Suzuki S, Nagamura Y, Shinohara R and
`Ishiguro I 1976 An enzyme immunosensor for IgG J. Solid-Phase Biochem. 1
`319-28
`[ 14) Wohltjen Hand Dessey R 1979 Surface acoustic wave probe for chemical analysis
`I. Introduction and instrument description Anal. Chem. 51 1458-64
`[15) Schultz JS, Mansouri Sand Goldstein I J 1982 Affinity glucose sensor Diabetes
`Care 5 245-53
`[ 16) Carter F L 1983 Molecular level fabrication techniques and molecular electronic
`devices J. Vac. Sci. Technol. B 1 959-68
`[ 17) Peterson J I, Goldstein S R, Fitzgerald R V and Buckhold D K 1980 Fiber optic
`pH