EP0273920A1 - Capacitive chemical sensor using an ion exchange surface - Google Patents

Capacitive chemical sensor using an ion exchange surface

Info

Publication number
EP0273920A1
EP0273920A1 EP87902201A EP87902201A EP0273920A1 EP 0273920 A1 EP0273920 A1 EP 0273920A1 EP 87902201 A EP87902201 A EP 87902201A EP 87902201 A EP87902201 A EP 87902201A EP 0273920 A1 EP0273920 A1 EP 0273920A1
Authority
EP
European Patent Office
Prior art keywords
counter
ions
ion
ion exchange
exchange layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP87902201A
Other languages
German (de)
French (fr)
Other versions
EP0273920A4 (en
Inventor
William D. Stanbro
Arnold L. Newman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Johns Hopkins University
Original Assignee
Johns Hopkins University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Johns Hopkins University filed Critical Johns Hopkins University
Publication of EP0273920A4 publication Critical patent/EP0273920A4/en
Publication of EP0273920A1 publication Critical patent/EP0273920A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/22Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating capacitance
    • G01N27/227Sensors changing capacitance upon adsorption or absorption of fluid components, e.g. electrolyte-insulator-semiconductor sensors, MOS capacitors
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3276Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a hybridisation with immobilised receptors

Definitions

  • Figure 10 is an embodiment of the differential capacitive sensor having the ion exchange capacitive sensor and the reference capacitor located back to back.
  • the liquid medium 20 may be an aqueous solution and the counter-ions 22 may include certain protein or fatty acid molecules.
  • an equilibrium will be established between the counter-ions 22 attached to the surface of the ion exchange layer 18 and the counter-ions 22 remaining in the bulk solution. This equilibrium will reflect the ionic composition of the liquid medium.
  • Figure lb illustrates the ion exchange that occurs when an analyte 24.is added to the liquid medium. When an analyte 24 in sufficient concentration is introduced into the liquid medium, there will be competition with the counter-ions 22 for the functional charge sites on the surface of the ion exchange layer 18.
  • the ion. exchange capacitive sensor may be integrated with the reference capacitor and signal processing electronics to form either a monolithic integrated chip or a hybrid circuit.
  • the ion exchange capacitive sensor could be integrated in the gate circuit of a field effect transistor (FET) to yield a "floating gate” FET configuration.
  • FET field effect transistor

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Power Engineering (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)

Abstract

Le capteur chimique capacitif décrit utilise une couche d'échange d'ions (18), afin de détecter des ions (24) d'analyte dans un milieu liquide (20). Un mécanisme d'échange se produit sur la surface de la couche d'échange d'ions (18) dans lequel une partie des ions contraires (22) sont retirés de la surface au bénéfice d'ions d'analyte (24). Le mouvement des ions contraires (22) ainsi produit s'éloignant de la surface de la couche d'échange d'ions (18) modifie la constante diélectrique du milieu liquide (20) le long de la surface de la couche d'échange d'ions (18). Cette modification de la constante diélectrique produit une modification de la capacitance du capteur chimique capacitif.The described capacitive chemical sensor uses an ion exchange layer (18) to detect analyte ions (24) in a liquid medium (20). An exchange mechanism occurs on the surface of the ion exchange layer (18) in which a portion of the opposing ions (22) are removed from the surface for the benefit of analyte ions (24). The movement of the opposing ions (22) thus produced moving away from the surface of the ion exchange layer (18) modifies the dielectric constant of the liquid medium (20) along the surface of the exchange layer d 'ions (18). This change in the dielectric constant produces a change in the capacitance of the capacitive chemical sensor.

Description

CAPACITIVE CHEMICAL SENSOR USING AN ION EXCHANGE SURFACE
STATEMENT OF GOVERNMENTAL INTEREST
The Government has rights in this invention pursuant to Contract No. N00024-85-C-5301, awarded by the Department of the Navy. BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a capacitive chemical sensor that uses an ion exchange surface to detect analyte ions in a liquid medium.
2. Description of the Prior Art
Various capacitive sensors are taught in the art to detect humidity in the air or anesthetic gas in a gas mixture delivered to a patient during various medical procedures. U.S. patent 3,350,941 issued to K.W. Misevich et al and U.S. patents 4,203,087 and 4,277,742 issued to Kovac et al, disclose capacitive humidity sensors. These humidity sensors use a moisture sensitive layer which absorbs water vapor. The dielectric property of the layer changes as it is penetrated by water vapors. As the moisture content of the air increases the capacitance of the humidity sensor increases.
U.S. patent 4,453,126 issued to G.A. Volgyesi and a publishe U.K. patent application GB 2 137 361 A, teach an apparatus for measuring anesthetic gas in a breathing mixture supplied to a patient. For both references, a planar capacitor is coated with polymeric or lipid layer. The physical or chemical properties of the polymeric or lipid layer change with increasing concentration of the anesthetic gas, causing a change in the dielectric constan of the layer.
Similarly, U.S. patent 4,264,331 issued to Klein et al discloses an air pollutant and/or fire combustion sensing apparatus using a capacitive sensor. Physical absorption of the analyte gas into a coating changes the dielectric properties of the coating.
A related U.S. patent application filed by Arnold L. Newman on November 19, 1985, entitled "Capacitive Chemical Sensor for Chemical Analysis and Measurement" (S.N. 799,716) discloses a capacitive chemical sensor utilizing biochemical bonding systems; another related application filed by the present inventors and entitled "Capacitive Chemical Sensor for Detecting Certain Analytes, including Hydrocarbons in a Liquid Medium" discloses a capacitive chemical sensor relying on the affinity of an "active layer" for analyte molecules in solution.
SUMMARY OF THE INVENTION The present invention is a new type of capacitive chemical sensor that utilizes an ion exchange, layer. The ion exchange layer may have strong cation exchange sites, weak cation exchange sites, strong anion exchange sites or weak anion exchange sites. The surface of the ion exchange layer is exposed to a liquid medium containing a counter-ion. The counter-ion is usually a relatively large ion compared to a water molecule and has a dielectric constant significantly different from the water molecules. The counter-ions in solution are in equilibrium with the counter-ions that are attached to the ion exchange layer. However, when smaller analyte ions are introduced into the liquid medium, equilibrium is disturbed and a portion of the counter-ion are removed from the surface of the ion exchange layer. Exchange of the counter-ions from the surface of the ion exchange layer causes the influx of higher dielectric water molecules into the volume once occupied by the counter-ions. As- a result, the dielectric properties of the liquid medium in the volume close to and above the ion exchange layer change, thus altering the measured capacitance of the sensor.
The invention uses an "open" or planar capacitor that comprises: a first and second conductor or electrode positioned on a substrate and dispose a distance from each other to form a channel; a first electrical insulating layer that covers the conductors; and, an ion exchange layer, which then coats the two insulated conductors and may fill a portion of the channel formed between the conductors. When an alternating voltage is applied across the conductors, an electric field is generated having lines of flux that cross the channel and bridge the volume between the conductors.
The present invention also teaches a differential sensor embodiment comprising the ion exchange capacitive sensor, as described above, with a reference capacitive sensor. The accuracy, of the present invention is increased if differential sensing is employed. The reference capacitor compensates for changes in the dielectric constant of the liquid medium caused by changes in temperature, general ionic concentration and the physical and chemical state of the liquid medium.
A first novel feature is the use of an ion exchange layer to alter the dielectric properties in the liquid medium above the surface of the ion exchange layer.
A second novel feature is the utilization of an ion exchange mechanism, wherein a portion of the counter-ions attached to the surface of an ion exchange layer are removed in response to an increase in analyte concentration; wherein the volume once occupied by the counter-ions adjacent to the ion exchange surface is filled with higher dielectric fluid molecules.
A third novel feature is the use of a differential sensor having an ion exchange capacitive sensor and a reference capacitive sensor. The reference capacitive sensor compensates for changes in the dielectric constant of the liquid medium caused by changes in temperature, general ionic concentration or other physical or chemical states of the liquid medium. BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic cross-sectional view of the invented capacitive chemical sensor using an ion exchange layer; Figure la illustrates the initial equilibrium condition; and. Figure lb illustrates displacement of the counter-ions from the surface of an ion exchange layer with the introduction of analyte into the liquid medium.
Figure 2 is a chemical diagram of a strong cation exchange layer. Figure 3 is a chemical diagram of a weak cation exchange layer.
Figure 4 is a chemical diagram of a strong anion exchange layer.
Figure 5 is a chemical diagram of a weak anion exchange layer.
Figure 6 is a perspective view of an "open" capacitor that uses a plurality of interdigitated fingers.
Figure 7 is a schematic cross-sectional view of the ion exchange capacitive sensor positioned in a protective casing. Figure 8 is a schematic cross-section view of a differential capacitive sensor comprising an ion exchange capacitive sensor and a reference capacitive sensor.
Figure 9 is an embodiment of the differential capacitive sensor having the ion exchange capacitive sensor and the reference capacitive sensor located side by side.
Figure 10 is an embodiment of the differential capacitive sensor having the ion exchange capacitive sensor and the reference capacitor located back to back.
Figure 11 is a schematic diagram of a circuit to detect the phase difference between the ion exchange capacitive sensor and the reference capacitor.
Figure 12 is a schematic diagram of a microprocessor system for use with a differential capacitive sensor that has an ion exchange capacitive sensor and a reference capacitive sensor. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Figures la and lb are schematic cross-sectional views showing the general configuration of the capacitive chemical sensor. A first conductor 10 and a second conductor 12 are positioned on the surface of an insulating material or substrate 14. A first layer containing an electrically insulated material 16 coats the two electrodes. An ion exchange layer 18 also coats the two electrodes and may partially fill the channel formed between the two electrodes. The ion exchange layer 18 is selected to have positive or negative sites and is exposed to a liquid medium 20 containing counter-ions 22 in solution. The counter-ions have an opposite sign from the positive or negative sites on the ion exchange layer. As' will be described later in this specification, the liquid medium 20 may be an aqueous solution and the counter-ions 22 may include certain protein or fatty acid molecules. As shown in Figure la, an equilibrium will be established between the counter-ions 22 attached to the surface of the ion exchange layer 18 and the counter-ions 22 remaining in the bulk solution. This equilibrium will reflect the ionic composition of the liquid medium. Figure lb illustrates the ion exchange that occurs when an analyte 24.is added to the liquid medium. When an analyte 24 in sufficient concentration is introduced into the liquid medium, there will be competition with the counter-ions 22 for the functional charge sites on the surface of the ion exchange layer 18. A portion of the counter-ions 22 which had been attached to the ion exchange layer 18 will be released into the bulk solution and exchanged for analyte ions. The composition of ions bound to the surface of the ion exchange layer 18 thus changes. The resulting ion exchange modifies the dielectric constant of the liquid medium adjacent to the surface of the ion exchange layer 18.
When an alternating voltage is applied across the electrodes (10, 12), an electric field is generated having electrical lines of flux 26. The electric field will be larger within the channel and near the electrodes, and will decrease as one moves away from the electrodes. The capacitance of the sensor varies as the ion exchange mechanism changes the dielectric constant of the liquid medium in these higher field regions. The capacitance change can be measured using known electronic apparatus, such as a GenRad 1657 RLC Digibridge. Two possible mechanism account, for the change in the dielectric constant within this electric field region. The first mechanism involves moving molecules of water into the region of high electric field intensity. The counter- ions 22 are generally larger than the water molecules (by an order of 102 to 104, or larger) and generally have a dielectric constant significantly smaller than water. When the counter-ions are attached to. he surface of the ion exchanged layer 18, they displace water molecules from this region. The analyte ions 24 are generally significantly smaller than the counter-ions 22 and displace less water molecules. As discussed above, the ion exchange mechanism causes the movement of the larger counter-ions 22 from the surface of the ion exchange layer 18 back into bulk solution. This movement causes the higher dielectric water molecules to fill the volume previously occupied by counter-ions near the surface of the ion exchange layer 18. This movement of water molecules into the higher field region near the surface of the ion exchange layer 18 from the lower field regions in the bulk solution, increases the dielectric constant and increases the measured capacitance of the sensor. To maximize the change in capacitance for increasing analyte concentration, one would choose a counter-ion 22 with a large volume compared to the fluid molecules and with a dielectric constant significantly different from the fluid molecules.
The second mechanism, involves the replacement of a portion of the counter-ions 22, having a first dielectric constant, with analyte ions, having a second significantly different dielectric constant. As discussed previously, the ion exchange mechanism causes a portion of the counter-ions to be displaced from the surface of the ion exchange layer 18 and a portion of the analyte ions to attach to the surface of the ion exchange layer 18. For example, exchanging lower dielectric counter-ions 22 for higher dielectric analyte ions 24, will increase the measured capacitance.
Figures 2 through 4 show four different types of ion exchange layers; (1) a strong acid cation exchange layer is shown in Figure 2; (2) a weak acid cation exchange layer is shown in Figure 3; (3) a strong anion exchange layer is shown in Figure 4; and (4) a weak anion exchange layer is shown in Figure 5. Production of all four layers starts with coating the surface electrodes (10, 12) with an electrically insulating layer, such as SiO, and then- coating the insulating layer with a molecular linking chain. Applicants suggest the following procedure, although it is to be understood that this procedure is merely by way of example and that other linking groups could be used with a different derivatization procedure: 1. The conductors of the capacitive chemical sensor are coated with a 0.3 micron thick layer of SiO; and,
2. Propyla ine groups are attached to the SiO surface layer, using the following steps: a. soak the substrate in 10% aminopropyl-triethoxysilane
I(EtO)3-Si-(CH2)3-NH2] and dry toluene overnight at room temperature, b. wash with dry toluene; and c. dry at 60 C for 2 hours.
To produce the strong cation exchange layer shown in Figure 2, the surface derivatized with the linking group 28 (such as the amino linking group outlined above) is reacted with benzene disulfonyl chloride to produce a sulfonamide linkage between the amine linking group and the benzene ring. The other, unreacted sulfonyl chloride group can then be hydrolyzed to sulfonic acid, which forms the cation exchange site 30. Applicants suggest, by way of example, the following procedure:
1. Cover the surface of the capacitive chemical sensor previously derivatized with an amine linking group, with a solution of lg of benzene disulfonyl chloride in 10 ml of pyridine.
2. Allow to sit for 30 minutes and then rinse thoroughly with distilled water. The resulting strong acid cation exchange layer, shown in Figure 2, comprises a linking group 28 and a cation exchange site 30. The cation exchange site 30 is negatively charged and will attract a positive counter ion 22 (see generally Figure lb). The strong cation exchange layer would be used to detect positive analyte ions in the liquid medium. It of course is to be understood, that other linking groups and other cation exchange groups can be used to form the cation exchange layer 18. Figure 3 illustrates a typical weak acid cation exchange layer comprising a linking group 28 and a cation exchange site 32. To produce this layer, the surface of the capacitive sensor is first derivatized with a linking group, such as the amino linking group described above. The derivatized surface is then reacted with . excess succinyl chloride to form an amide linkage between the amino linking group 28 and. the succinyl group. ' The unreacted acid chloride portion can then be hydrolyzed to a carboxylate group. At a sufficiently high pH the carboxylic acid is ionized forming the cation exchange site 32. Applicants suggest, by way of example, the following procedure:
1. Cover the surface of the capacitive chemical sensor previously derivatized with an amino linking group, with a solution of lg of succinyl chloride in 10 ml of pyridine.
2. Allow it to sit for 30 minutes and then rinse thoroughly with distilled water. The cation exchange layer produced in this manner is considered "weak" because the acid only becomes partially ionized. This ion exchange layer has a cation exchange site 32 that is negatively charged and will attract a positive ion 22 (see generally Figure lb). The weak cation exchange layer, shown in Figure 3, could be used to detect positive ions in the liquid medium. It of course is to be understood, that other linking groups and other cation exchange groups can be used to form the weak cation exchange layer.
Figure 4 illustrates a typical anion exchange layer comprising a linking group 28 and an anion exchange site 34. To produce this layer, the surface of the capacitive sensor is first derivatized with a linking group, such as the amino linking group outlined above. The derivatized surface is then reacted with iodomethane until it is exhaustively methylated. This results in the formation of a tetramethyl quarternary ammonium salt that has a positive charge and therefore forms the ion exchange site 34. Applicants suggest, by way of example, the following procedure:
1. Cover the surface of the capacitive chemical sensor previously derivatized with an amino linking group, with iodomethane.
2. Heat gently for 10 minutes and then cool to room temperature and rinse twice with ethanol.
The ion exchange layer thus produced has an anion- exchange site 34. that is positively charged and will attract a negative counter ion 22 (see, generally Figure lb). The anion exchange layer, shown in Figure 4, would be used to detect negative ions in the liquid medium. It is of course to be understood, that other linking groups and other anion exchange groups can be used to form the anion exchange layer. Figure 5 illustrates a typical weak anion exchange layer comprising a linking group 28 and weak anion exchange site 35. To produce this layer, the surface of the capacitive sensor is first derivatized with the amino linking group, as described above. In a sufficiently low pH medium, the amino group becomes ionized. This forms the weak anion exchange sites 35.
The anion exchange layer produced in this manner is considered "weak" because the amino group only becomes partially ionized. This ion exchange layer has anion exchange sites 35 tha are positively charged and will attract a negative ion 22 (see generally Figure lb). The weak anion exchange layer, shown in Figure 5, could be used to detect negative ions in the liquid medium. It of course is to be understood, that other linking groups and other weak anion exchange groups can be used to form the weak anion exchange layer.
As best shown in Figure 1A, the capacitive chemical sensor i preloaded with a liquid medium 20 containing counter-ions 22 in solution. Applicants have found that protein molecules or fatty acids provide excellent counter-ions. Protein molecules contain carboxylic acid groups and amino groups. With appropriate pH levels, the carboxylic acid groups will carry a negative charge and will be attracted to an anion exchange layer. Similarly, wit appropriate pH levels, the amino groups will carry a positive charge, and will be attracted to a cation exchange layer. Fatty acids contain carboxylic acid groups, and with the correct pH, will carry a negative charge. These counter-ions were chosen because they are large compared to water molecules and have a dielectric constant lower than water. Typical protein molecules would be 102 to 104'or' more, times iarger than a water molecule; and, fatty acids would be 101 to 102 times larger than water molecules. However, it is to be understood that other counter- ions could be used and that the response of the sensor would be maximized when the counter-ions are considerably larger than wate molecules and have a dielectric constant significantly different from water molecules. Similarly, a detection system could be made with counter-ions and analyte ions of the same size, if their dielectric constants are significantly different. In operation, sensor preloaded with large protein molecules (which have both cation and anion groups on it) would respond with an increase in capacitance if a portion of the protein molecules were displaced by a small analyte ion such as a chloride ion.
Figure 6 is a perspective view of a planar capacitor having plurality of interdigitated fingers. Metallic electrodes or conductors 36 and 38 are positioned on an insulating substrate 40 Each electrode has a plurality of fingers that are disposed in an interdigitated manner relative to the fingers of the other electrodes. The interdigitated fingers from both electrodes form a plurality of channels. Known photolithographic etching techniques are used to form the interdigitated fingers on a substrate. The substrate can be made from insulating material such as Corning 7059 glass or alumina wafers. The interdigitated fingers can be made of copper or gold. Applicants selected 2 mil wide fingers that are approximately 1 mil high and separated by 3 mil spaces, although other dimensions maybe used. The interdigitated fingers are covered with an insulating layer 42. Applicants made the insulating layer 42 with a 1-2.5 micron coating of parylene polymer deposited using known deposition processes and a 0.3 micron coating of SiO deposited using vapor vacuum evaporation deposition; however, alternative electrical insulating material can be used. To complete the sensor, an ion exchange layer coats the insulating layer 42. (The ion exchange layer 18 is best shown in Figure la). Liquid to be tested for a particular analyte ion is brought into contact with the planar capacitor as discussed earlier. It is to be understood that othe geometries of the planar capacitor can provide the desired featur of the open capacitor. For example, the electrode elements of th capacitor can be interleaved on a substrate or, parallel electrod elements can be embedded in a molded insulator with the ion exchange layer coating the molded insulator. Further, the electrode elements 36 and 38 of the capacitor can be made from electrically conductive material or doped semiconductor materials such as doped silicon. \
It* is also to be understood that, the invention will work with aqueous solutions that have different salt contents. Further it is to be understood that the liquid medium may be nonaqueous liquids, as long as a significant dielectric change will occur with the displacement of those liquid molecules by the mechanisms taught herein. Figure 7 is a schematic representation of the planar capacitor 44 (designed in accordance with the specification) and securely fixed in a casing 46. A molecular sieve membrane 48 allows solutions to enter the interior of the casing from the environment and to contact the sensor 44. The molecular sieve membrane 48 protects the sensor from abrasive particles in the environment and prevents the larger counter-ions from escaping from the casing, thereby allowing continuous or time trend measurements. Figure 8 is a schematic representation of a differential sensor embodiment that includes both the ion sensor 44 and the reference capacitor 50. The accuracy of the present invention is increased.if differential sensing is used. The reference capacitor 50 compensates for changes in the dielectric of the liquid medium caused by changes in temperature, ionic concentration, pH, composition and the physical and chemical state of the liquid medium. The reference capacitor 50 is identical in design to the ion exchange sensor capacitor, except the ion exchange layer is not used. Therefore, the reference capacitor comprises two electrodes positioned on a substrate coated with an insulating layer to form a capacitor. In the embodiment shown in Figure 8, the ion exchange capacitive sensor 44 and the reference capacitor 50 are mounted within casing 52. A molecular sieve membrane 54 allows solutions to enter the interior of the casing from the environment and to contact both ion exchange capacitive sensor 44 and reference capacitor 50. The molecular sieve membrane 54 protects the sensor from abrasive particles in the environment and prevents the large counter-ions from escaping from the casing, thereby allowing continuous or time trend measurements.
Figures 9 and 10 show various embodiments for a differential sensor that includes an ion exchange capacitive sensor 44 and a reference capacitor 50. Figure 9 is a top view of the ion exchange capacitive sensor 44 and reference capacitor 50 located side by side on the same substrate. Figure 10 is a cross- sectional view of the ion exchange capacitive sensor 44 and reference capacitor 50 located back to back. A shield 56 located between the capacitors can be used to isolate the electric field generated by each capacitor. With both the side by side and back to back embodiments, the fluid medium under test is adapted to contact the surface of both the ion exchange sensor capacitor 44 and reference capacitor 50. For simplicity of illustration, the ion exchange capacitive sensor shown in Figures 9 and 10 do not show the ion exchange layer that covers the insulating layer. Figures 11 and 12 are schematic diagrams which illustrate two possible circuits to be used with a differential sensor as taught by the present invention. Figure 11 is a schematic diagram of the circuit to detect the phase difference between the ion exchange capacitive sensor 44 and the reference capacitor 50. The stable oscillator 58 supplies an alternating signal to the ion exchange capacitor 44 and the reference capacitor 50. These capacitors are placed in parallel with trim capacitors 60 and 62. Phase detector 64 detects the phase angle shift between the ion exchange capacitive sensor 44 and the reference capacitor 53. The phase shift is functionally related to the analyte ion concentration in the fluid medium.
Figure 12 is a schematic diagram of a microprocessor system for use with a differential sensor. The system contains an ion exchange capacitive sensor 44 and reference capacitor 50. The ion exchange capacitive sensor 44 and reference capacitor 50 are brought into contact with the liquid medium under test. Each capacitor is connected to an oscillator (66, 68) and a change in the capacitance will alter the frequency of oscillation of its associated oscillator. The output frequency of each oscillator (66, 68) is fed to an associated counter (70, 72), which sends the frequency count in digital form via bus 74 to microprocessor 76* A look-up table is stored in the microcomputer and a determination of the concentration of the analyte in the fluid medium is made. This value is displayed on output display 78. It is to be understood that other circuits can also be envisioned once one understands the differential change in capacitance between the ion exchange capacitor and the reference capacitor as taught the present invention. The ion. exchange capacitive sensor may be integrated with the reference capacitor and signal processing electronics to form either a monolithic integrated chip or a hybrid circuit. For example, the ion exchange capacitive sensor could be integrated in the gate circuit of a field effect transistor (FET) to yield a "floating gate" FET configuration. Obviously many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than is specifically described.

Claims

What is claimed is:
1. A device for sensing analyte ions in a liquid medium, comprising: an ion exchange layer, adapted to be exposed to a liquid medium containing counter-ions in solution, wherein a portion of said counter-ions attach to the surface of said ion exchange layer; and, a means, positioned in association with said ion exchange layer, responsive to displacement of said counter-ions from the surface of said ion exchange layer in response to the introduction of analyte ions into the liquid medium.
2. The device of claim 1, wherein said responsive means is a capacitor and wherein displacement of said counter-ions from the surface of said ion exchange layer alters the capacitance of said capacitor.
3. The device of claim 2, wherein said capacitor comprises at least one pair of spaced apart electrode elements.
4. The device of claim 1, wherein said ion exchange layer comprises a cation exchange site and wherein said counter-ion carries a positively charged site.
5. The device of claim 1, wherein said ion exchange layer comprises an anion exchange site and wherein said counter-ion carries a negatively charged site.
6. The device of claim 1, wherein said counter-ion is selected from the group consisting of protein molecules and fatty acids.
7. The device of claim 1, wherein said counter-ion is large compared to water molecules and has a lower dielectric constant than water molecules.
8. The device of claim 7, wherein said counter-ion is larger than the analyte ion.
9. The device of claim 3, wherein said electrode elements are made from doped semiconductor material.
10. The device of claim 3, wherein said electrode elements are made from electrically conductive material.
11. The device of claim 3, wherein an electrically insulating material separates said at least one pair of electrode elements from said ion exchange layer. _ J5_
12. The device of claim 2, further comprising an electronic means, operably coupled to said capacitor, for measuring and displaying a change in capacitance.
13. A device for sensing analyte ions in a liquid comprising: a plurality of counter-ions in a liquid medium; a capacitor having at least one pair of spaced apart electrode elements, said electrode elements adapted to create an electric field therebetween; an electrically insulating layer coating said electrode elements; an ion exchange layer coating said electrically insulating layer and at least partially filling the volume between said electrode elements, said ion exchange layer adapted to be exposed to said counter-ions so that a portion of said counter-ions attach to the surface of said ion exchange layer and wherein introduction of analyte ions into the liquid medium results in displacement of a percentage of the counter-ions from the surface of said ion exchange layer.
14. The device of claim 13, wherein counter-ions are displaced from the surface of said ion exchange layer in proportion to increased analyte ion concentration, whereby a change in capacitance of the device indicates a change in analyte concentration.
15. The device of claim 13, wherein said ion exchange layer comprises a cation exchange site and wherein said counter ion carries a positively charged site.
16. The device of claim 13, wherein said ion exchange layer comprises an anion exchange site and wherein said counter-ion carries a negatively charged site.
17. The device of claim 13, wherein each of said electrode elements comprises a plurality of spaced apart finger electrodes.
18. The device of claim 13, wherein said capacitor is positioned in the chamber of a casing, said chamber being at least partially filled with a liquid medium containing said plurality of counter-ions.
19. The device of claim 18, wherein said chamber includes. an opening exposed to liquid containing analyte ions.
20. The device of claim 19, wherein a membrane covers said opening, said membrane having pores sized to prevent escape of counter-ions from said chamber.
21. The device of claim 13, wherein said counter-ion is selected from the group consisting of protein molecules and fatty acids.
22. The device of claim 13, wherein said counter-ion is large compared to water molecules and has a lower dielectric constant than water molecules.
23. The device of claim 13, wherein said counter-ion is larger than the analyte ion.
24. The device of claim 13, wherein said electrode elements are made from doped semiconductor material.
25. The device of claim 13, wherein said electrical elements are made from electrically conductive material.
26. The device of claim 13, further comprising an electronic means, operably coupled to second capacitor, for measuring and displaying a change in capacitance.
27. A differential sensor for sensing analyte ions in a liquid, comprising: a first capacitor having at least one pair of spaced apart electrode elements; an ion exchange layer positioned in association with said electrode elements of said first capacitor and adapted to be exposed to a liquid medium; a plurality of counter-ions in the liquid medium; a second capacitor having at least one pair of spaced apart electrode elements; a layer of electrically insulating material coating said spaced apart electrode elements of said second capacitor and adapted to be exposed to the liquid medium; and, an electronic means, operably coupled to said first and second capacitor for calculating the analyte concentration of the liquid medium, wherein the introduction of analyte ions into the liquid medium will displace a portion of said counter-ions from the surface of said ion exchange layer thereby changing the capacitance of said first capacitor.
28. The device of claim 27, wherein an electrically insulating material separates said electrode elements of said first capacitor from said ion exchange layer.
29. The device of claim 27, wherein said first and second capacitor are positioned in the chamber of a casing, said chamber containing liquid medium containing said counter-ions.
30. The device of claim 29, wherein said chamber includes an opening exposed to a liquid containing analyte ions.
31. The device of claim 30, wherein a membrane covers said opening, said membrane having pores sized to prevent escaped counter-ions from said chamber.
32. The device of claim 27, wherein said counter-ion is selected from the group consisting of protein molecules and fatty acids.
33. The device of claim 27, wherein said counter-ion is large compared to water molecules and has a lower dielectric constant than water molecules.
34. The device of claim 27, wherein said counter-ion is larger than the analyte ion.
35. The device of claim 27, wherein said electrode elements for said first and second capacitor are made from doped semiconductor material.
36. The device of claim 27, wherein said electrodes elements for said first and second capacitor are made from electrically conducted material.
37. The device of claim 27, wherein said ion exchange layer comprises a cation exchange side and wherein said counter-ion carries a positively charged site.
38. The device of claim 27, wherein said ion exchange layer comprises an ion exchange site and wherein said counter-ion carries a negatively charged site.
EP87902201A 1986-04-01 1987-02-27 Capacitive chemical sensor using an ion exchange surface Withdrawn EP0273920A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US84707386A 1986-04-01 1986-04-01
US847073 1997-04-30

Publications (2)

Publication Number Publication Date
EP0273920A4 EP0273920A4 (en) 1988-06-08
EP0273920A1 true EP0273920A1 (en) 1988-07-13

Family

ID=25299684

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87902201A Withdrawn EP0273920A1 (en) 1986-04-01 1987-02-27 Capacitive chemical sensor using an ion exchange surface

Country Status (4)

Country Link
EP (1) EP0273920A1 (en)
JP (1) JPS63502930A (en)
CA (1) CA1256944A (en)
WO (1) WO1987006002A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9103053D0 (en) * 1991-02-13 1991-03-27 Univ Guelph Solution phase ion and water sensitive detector
IL116921A (en) 1996-01-26 2000-11-21 Yissum Res Dev Co Electrochemical system for determination of an analyte in a liquid medium
US7163659B2 (en) * 2002-12-03 2007-01-16 Hewlett-Packard Development Company, L.P. Free-standing nanowire sensor and method for detecting an analyte in a fluid
JP7234843B2 (en) * 2018-11-16 2023-03-08 ミネベアミツミ株式会社 DETECTION DEVICE AND CHARGE-VOLTAGE CONVERSION CIRCUIT

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4520341A (en) * 1981-12-08 1985-05-28 Sharp Kabushiki Kaisha Moisture responsive element with crosslinked organic membrane and protective layering
US4562725A (en) * 1982-07-31 1986-01-07 Shimadzu Corporation Moisture sensor and a process for the production thereof
US4571543A (en) * 1983-03-28 1986-02-18 Southwest Medical Products, Inc. Specific material detection and measuring device

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8706002A1 *

Also Published As

Publication number Publication date
EP0273920A4 (en) 1988-06-08
CA1256944A (en) 1989-07-04
WO1987006002A1 (en) 1987-10-08
JPS63502930A (en) 1988-10-27

Similar Documents

Publication Publication Date Title
US4935207A (en) Capacitive chemical sensor using an ion exchange surface
CA1251516A (en) Capacitive chemical sensor for detecting certain analytes, including hydrocarbons in a liquid medium
US5114674A (en) Added array of molecular chains for interfering with electrical fields
EP0906562B1 (en) Detection of ligand interaction with polymeric material
US4822566A (en) Optimized capacitive sensor for chemical analysis and measurement
EP0100661B1 (en) Moisture sensor and a process for the production thereof
US4238757A (en) Field effect transistor for detection of biological reactions
US5567301A (en) Antibody covalently bound film immunobiosensor
US4916075A (en) Differential homogeneous immunosensor device
EP0894265A1 (en) Biosensors
PT84810B (en) PROCESS FOR THE DETECTION AND / OR IDENTIFICATION OF A BIOLOGICAL SUBSTANCE IN A LIQUID WITH THE ASSISTANCE OF ELECTRICAL MEASURES AND A DEVICE INTENDED FOR IN PRACTICE THIS PROCESS
US6111342A (en) Instrument for chemical measurement
GB2136130A (en) Chemical Assay Systems
EP0273920A1 (en) Capacitive chemical sensor using an ion exchange surface
US5479716A (en) Capacitive based gravity sensor
KR102083485B1 (en) Biosensor for detecting cortisol using resistance switching and hysteresis change, method for preparing thereof and application thereof
JPH0326345B2 (en)
JP2540689B2 (en) Biological capacitance sensor
SU1691781A1 (en) Transducer for measuring specific capacitance of foil
SU868483A1 (en) Device for determining kinetics of permeability of chemically active substances through polymers
Takahashi Moisture Intrusion in Sio2/Epoxy Interfaces
JPS6018768A (en) Non-contact type conductivity/dielectric constant simultaneous measuring sensor
RU94038579A (en) Resistive gas detector
JPS62145128A (en) Temperature sensor

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19880405

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT CH DE FR GB IT LI NL SE

A4 Supplementary search report drawn up and despatched

Effective date: 19880608

17Q First examination report despatched

Effective date: 19900112

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19910406

R18W Application withdrawn (corrected)

Effective date: 19910406

RIN1 Information on inventor provided before grant (corrected)

Inventor name: STANBRO, WILLIAM, D.

Inventor name: NEWMAN, ARNOLD, L.