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US5959191A Expired / Lapsed US ⏱️ 0.0 years remaining

Sensor arrays for detecting analytes in fluids

Assignee: California Institute of Technology
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Filing: 1998-01-13
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Granted: 1999-09-28
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Expires: 2018-01-13
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Abstract

Abstract Chemical sensors for detecting analytes in fluids comprise first and second conductive elements (e.g. electrical leads) electrically coupled to and separated by a chemically sensitive resistor which provides an electrical path between the conductive elements. The resistor comprises a plurality of alternating nonconductive regions (comprising a nonconductive organic polymer) and conductive regions (comprising a conductive material) transverse to the electrical path. The resistor provides a difference in resistance between the conductive elements when contacted with a fluid comprising a chemical analyte at a first concentration, than when contacted with a fluid comprising the chemical analyte at a second different concentration. Arrays of such sensors are constructed with at least two sensors having different chemically sensitive resistors providing dissimilar such differences in resistance. Variability in chemical sensitivity from sensor to sensor is provided by qualitatively or quantitatively varying the composition of the conductive and/or nonconductive regions. An electronic nose for detecting an analyte in a fluid may be constructed by using such arrays in conjunction with an electrical measuring device electrically connected to the conductive elements of each sensor.

Inventors

  • 👤 Nathan S. Lewis
  • 👤 Michael S. Freund

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-31 12:48
CPC Classifications
G; G01; G01N; G01N27/00; G01N27/02; G01N27/04; G01N27/12; G01N27/125; G01N27/126; G01N33/00; G01N33/0004; G01N33/0009; G01N33/0027; G01N33/0031; G01N33/48; G01N33/483; G01N33/497; Y; Y10; Y10S; Y10S435/00; Y10S435/817

Claims Analysis

Total Claims: 63
Claim 1
Independent Claim 189 words
A sensor for detecting an analyte in a fluid comprising: a first chemically sensitive resistor comprising a first blend of a first nonconductive polymer and nonconductive polymer, and a conductive material arranged in a matrix of non-conductive and conductive regions; a second chemically sensitive resistor comprising a second blend of a first nonconductive polymer and nonconductive polymer, and a conductive material arranged in a matrix of non-conductive and conductive regions; a conductive material; electrical measuring apparatus electrically connected to said first resistor and to said second resistor, wherein during use, the permeation of the first blend of nonconductive polymers by the analyte in the first chemically sensitive resistor produces a first resistance which is different from a baseline resistance of the first resistor, the permeation of the second blend of nonconductive polymers by the analyte in the second chemically sensitive resistor produces a second resistance which is different from a baseline resistance of the second resistor, and wherein the difference between the first resistance and the baseline resistance of the first resistor is different from the difference between the second resistance and the baseline resistance of the second resistor.
Claim 2
Dependent Claim 189 words
A sensor for detecting an analyte in a fluid comprising: a first chemically sensitive resistor comprising a first blend of a first nonconductive polymer and nonconductive polymer, and a conductive material arranged in a matrix of non-conductive and conductive regions; a second chemically sensitive resistor comprising a second blend of a first nonconductive polymer and nonconductive polymer, and a conductive material arranged in a matrix of non-conductive and conductive regions; a conductive material; electrical measuring apparatus electrically connected to said first resistor and to said second resistor, wherein during use, the permeation of the first blend of nonconductive polymers by the analyte in the first chemically sensitive resistor produces a first resistance which is different from a baseline resistance of the first resistor, the permeation of the second blend of nonconductive polymers by the analyte in the second chemically sensitive resistor produces a second resistance which is different from a baseline resistance of the second resistor, and wherein the difference between the first resistance and the baseline resistance of the first resistor is different from the difference between the second resistance and the baseline resistance of the second resistor.
Claim 3
Dependent Claim 30 words
The sensor of claim 1, wherein said first nonconductive polymer in said first chemically sensitive resistor is the same as said first nonconductive polymer in said second chemically sensitive resistor.
Claim 4
Dependent Claim 30 words
The sensor of claim 1, wherein said second nonconductive polymer in the first chemically sensitive resistor is the same as said second nonconductive polymer in the second chemically sensitive resistor.
Claim 5
Dependent Claim 18 words
The sensor of claim 1, wherein the first nonconductive polymer and the second nonconductive polymer are organic polymers.
Claim 6
Dependent Claim 14 words
The sensor of claim 1, wherein the conductive material is an organic conducting polymer.
Claim 7
Dependent Claim 13 words
The sensor of claim 1, wherein the conductive material is a carbonaceous material.
Claim 8
Dependent Claim 14 words
The sensor of claim 1, wherein the conductive material is a charge transfer complex.
Claim 9
Dependent Claim 13 words
The sensor of claim 1, wherein the conductive material is an inorganic conductor.
Claim 10
Dependent Claim 15 words
The sensor of claim 1, wherein the conductive material is a mixed inorganic organic conductor.
Claim 11
Dependent Claim 13 words
The sensor of claim 1, wherein the conductive material is a doped semiconductor.
Claim 12
Dependent Claim 14 words
The sensor of claim 1, wherein the conductive material is a conductive metal oxide.
Claim 13
Dependent Claim 12 words
The sensor of claim 1, wherein the conductive material is a superconductor.
Claim 14
Dependent Claim 17 words
The sensor of claim 1, further comprising an information storage device coupled to said electrical measuring apparatus.
Claim 15
Dependent Claim 14 words
The sensor of claim 1, wherein said electrical measuring apparatus includes an integrated circuit.
Claim 16
Dependent Claim 42 words
The sensor of claim 2, wherein concentration of the first nonconductive polymer in the first blend of the first chemically sensitive resistor is different from the concentration of the first nonconductive polymer in the second blend of the second chemically sensitive resistor.
Claim 17
Dependent Claim 33 words
The sensor of claim 4, wherein the first nonconductive polymer is selected from the group consisting of poly(styrene), poly(a-methyl styrene), poly(n-vinyl pyrrolidone), poly(4-vinyl phenol), poly(vinyl butral), poly(vinyl acetate), and poly(bis phenol A carbonate).
Claim 18
Dependent Claim 23 words
The sensor of claim 4, wherein the second nonconductive polymer is selected from the group consisting of poly(acrylonitrile), poly(maleic anhydride), and poly(allyl alcohol).
Claim 19
Dependent Claim 33 words
The sensor of claim 4, wherein the first nonconductive polymer and the second nonconductive polymer are selected from the group consisting of main-chain carbon polymers, main-chain acyclic heteroatom polymers and main-chain heterocyclic polymers.
Claim 20
Dependent Claim 38 words
The sensor of claim 18, wherein the main-chain carbon polymer is selected from the group consisting of polydienes, polyalkenes, polyacrylics, polymethacrylics, polyvinyl ethers, polyvinyl thioethers, polyvinyl alcohols, polyvinyl ketones, polyvinyl halides, polyvinyl nitriles, polyvinyl esters, polystyrenes and polyarylenes.
Claim 21
Dependent Claim 35 words
The sensor of claim 18, wherein the main-chain acyclic heteroatom polymer is selected from the group consisting of polyoxides, polycarbonates, polyesters, polyanhydrides, polyurethanes, polysulfonates, polysiloxanes, polysulfides, polythioesters, polysulfones, polysulfonamides, polyamides, polyureas, polyphosphazenes, polysilanes and polysilazanes.
Claim 22
Dependent Claim 48 words
The sensor of claim 18, wherein the main-chain heterocyclic polymer is selected from the group consisting of polyfuran tetracarboxylic acid diimides, polybenzoxazoles, polyoxadiazoles, polybenzothiazinophenothiazines, polybenzothiazoles, polypyrazinoquinoxalines, polypyromellitimides, polyquinoxalines, polybenzimidazoles, polyoxindoles, polyoxoisoindolines, polydioxoisoindolines, polytriazines, polypyridazines, polypiperazines, polypyridines, polypiperidines, polytriazoles, polypyrazoles, polypyrrolidines, polycarboranes, polyoxabicyclononanes, polydibenzofurans, polyphthalides, polyacetals, polyanhydrides and carbohydrates.
Claim 23
Dependent Claim 22 words
The sensor of claim 5, wherein the organic conducting polymer is selected from the group consisting of polyanilines, polythiophenes, polypyrroles, and polyacetylenes.
Claim 24
Dependent Claim 24 words
The sensor of claim 6, wherein the carbonaceous material is selected from the group consisting of carbon blacks, graphite, coke and C 60 .
Claim 25
Dependent Claim 26 words
The sensor of claim 7, wherein the charge transfer complex is selected from the group consisting of tetramethylparaphenylenediamine-chloranile, alkali metal tetracyanoquinodimethane complexes and tetrathiofulvalene halide complexes.
Claim 26
Dependent Claim 20 words
The sensor of claim 8, wherein the inorganic conductor is selected from the group consisting of metals and metal alloys.
Claim 27
Dependent Claim 24 words
The sensor of claim 25, wherein the metal and metal alloys are selected from the group consisting of Ag, Au, Cu, Pt, and AuCu.
Claim 28
Dependent Claim 27 words
The sensor of claim 9, wherein the mixed inorganic organic conductor is selected from the group consisting of tetracyanoplatinate complexes, iridium halocarbonyl complexes, and stacked macrocyclic complexes.
Claim 29
Dependent Claim 26 words
The sensor of claim 10, wherein the doped semiconductor is selected from the group consisting of Si, GaAs, InP, MoS 2 , and TiO 2 .
Claim 30
Dependent Claim 33 words
The sensor of claim 11, wherein the conductive metal oxide is selected from the group consisting of In 2 O 3 , SnO 2 , and Na x Pt 3 O 4 .
Claim 31
Dependent Claim 33 words
The sensor of claim 12, wherein the superconductor is selected from the group consisting of YBa 2 Cu 3 O 7 , Ti 2 Ba 2 Ca 2 Cu 3 O 10 .
Claim 32
Dependent Claim 13 words
The sensor of claim 13, wherein said information storage device is a computer.
Claim 33
Dependent Claim 13 words
The method of claim 14, wherein said integrated circuit includes neural network-based hardware.
Claim 34
Dependent Claim 13 words
The method of claim 14, wherein said integrated circuit includes a digital-analog converter.
Claim 35
Independent Claim 230 words
A method for detecting the presence of an analyte in a fluid, comprising the steps of: providing a first chemically sensitive resistor having a baseline resistance, a first measured resistance response to permeation by said fluid and a first resistance response to permeation by said analyte, said first chemically sensitive resistor comprising a mixture of a nonconductive polymer and a conductive material; providing a second chemically sensitive resistor having a baseline resistance, a second measured resistance response to permeation by said fluid and a second resistance response to permeation by said analyte, said second chemically sensitive resistor comprising a mixture of a nonconductive polymer and a conductive material; providing an electrical measuring apparatus electrically connected to the first resistor and to the second resistor; exposing the first resistor and the second resistor to the fluid; measuring said first resistance response that occurs when the first resistor is permeated by the fluid, and said second resistance response that occurs when the second resistor is permeated by the fluid; comparing the first measured resistance response to the first resistance response to permeation by the analyte to generate a first indicator which indicates the presence of the analyte in the fluid, and comparing the second measured resistance response to the second resistance response to permeation by the analyte to generate a second indicator which indicates the presence of the analyte in the fluid.
Claim 36
Independent Claim 230 words
A method for detecting the presence of an analyte in a fluid, comprising the steps of: providing a first chemically sensitive resistor having a baseline resistance, a first measured resistance response to permeation by said fluid and a first resistance response to permeation by said analyte, said first chemically sensitive resistor comprising a mixture of a nonconductive polymer and a conductive material; providing a second chemically sensitive resistor having a baseline resistance, a second measured resistance response to permeation by said fluid and a second resistance response to permeation by said analyte, said second chemically sensitive resistor comprising a mixture of a nonconductive polymer and a conductive material; providing an electrical measuring apparatus electrically connected to the first resistor and to the second resistor; exposing the first resistor and the second resistor to the fluid; measuring said first resistance response that occurs when the first resistor is permeated by the fluid, and said second resistance response that occurs when the second resistor is permeated by the fluid; comparing the first measured resistance response to the first resistance response to permeation by the analyte to generate a first indicator which indicates the presence of the analyte in the fluid, and comparing the second measured resistance response to the second resistance response to permeation by the analyte to generate a second indicator which indicates the presence of the analyte in the fluid.
Claim 37
Dependent Claim 23 words
The method of claim 34, further comprising the step of comparing said first indicator and said second indicator to create a response pattern.
Claim 38
Dependent Claim 29 words
The method of claim 34, further comprising the steps of: providing an information storage device coupled to said electrical measuring apparatus; and storing information in said information storage device.
Claim 39
Dependent Claim 77 words
The method of claim 34, further comprising the steps of: comparing the first measured resistance response to said stored first resistance response to permeation by the analyte to generate a first storage-referenced indicator which indicates the presence of the analyte in the fluid; and comparing the second measured resistance response to said stored second resistance response to permeation by the analyte to generate a second storage-referenced indicator which indicates the presence of the analyte in the fluid.
Claim 40
Dependent Claim 14 words
The method of claim 34, wherein said electrical measuring apparatus includes an integrated circuit.
Claim 41
Dependent Claim 20 words
The method of claim 34, wherein the step of measuring the resistance response is performed using a multiplexing digital ohmmeter.
Claim 42
Dependent Claim 28 words
The method of claim 35, further comprising the step of using said response pattern to indicate the absence of a substance different from the analyte in the fluid.
Claim 43
Dependent Claim 13 words
The method of claim 35, wherein the information storage device is a computer.
Claim 44
Dependent Claim 37 words
The method of claim 35, wherein said stored information is the first resistance response to permeation by the analyte for said first resistor and the second resistance response to permeation by the analyte for said second resistor.
Claim 45
Dependent Claim 12 words
The method of claim 36, wherein said stored information is a database.
Claim 46
Dependent Claim 21 words
The method of claim 36, wherein said stored information is the resistance response of the resistor as a function of time.
Claim 47
Dependent Claim 36 words
The method of claim 37, further comprising the step of comparing said first storage-referenced indicator and said second storage-referenced indicator to create a storage-referenced response pattern that indicates the identity of the analyte in the fluid.
Claim 48
Dependent Claim 36 words
The method of claim 37, further comprising the step of comparing said first storage-referenced indicator and said second storage-referenced indicator to create a storage-referenced response pattern that indicates the concentration of the analyte in the fluid.
Claim 49
Dependent Claim 13 words
The method of claim 38, wherein said integrated circuit includes neural network-based hardware.
Claim 50
Dependent Claim 13 words
The method of claim 38, wherein said integrated circuit includes a digital-analog converter.
Claim 51
Independent Claim 262 words
A method for detecting the presence of an analyte in a fluid, comprising the steps of: providing a first chemically sensitive element having a first detectable measured response to permeation by said fluid and a first detectable response to permeation by said analyte, said first element comprising a first blend of first and second polymers and a conductive material arranged in a matrix of non-conductive and conductive regions; providing a second chemically sensitive element having a second detectable measured response to permeation by said fluid and a second detectable response to permeation by said analyte, said second element comprising a second blend of first and second polymers and a conductive material arranged in a matrix of non-conductive and conductive regions; providing a detector operatively associated with the first and second chemically sensitive elements; exposing the chemically sensitive elements to said fluid; measuring said first detectable measured response of the first element that occurs when the first element is permeated by the fluid, and said second detectable measured response of the second element that occurs when the second element is permeated by the fluid; comparing the first detectable measured response of the first element to said first detectable response to permeation by the analyte for the first element to generate a first indicator which indicates the presence of the analyte in the fluid; and comparing the second detectable measured response of the second element to said second detectable response to permeation by the analyte for the second element to generate a second indicator which indicates the presence of the analyte in the fluid.
Claim 52
Independent Claim 262 words
A method for detecting the presence of an analyte in a fluid, comprising the steps of: providing a first chemically sensitive element having a first detectable measured response to permeation by said fluid and a first detectable response to permeation by said analyte, said first element comprising a first blend of first and second polymers and a conductive material arranged in a matrix of non-conductive and conductive regions; providing a second chemically sensitive element having a second detectable measured response to permeation by said fluid and a second detectable response to permeation by said analyte, said second element comprising a second blend of first and second polymers and a conductive material arranged in a matrix of non-conductive and conductive regions; providing a detector operatively associated with the first and second chemically sensitive elements; exposing the chemically sensitive elements to said fluid; measuring said first detectable measured response of the first element that occurs when the first element is permeated by the fluid, and said second detectable measured response of the second element that occurs when the second element is permeated by the fluid; comparing the first detectable measured response of the first element to said first detectable response to permeation by the analyte for the first element to generate a first indicator which indicates the presence of the analyte in the fluid; and comparing the second detectable measured response of the second element to said second detectable response to permeation by the analyte for the second element to generate a second indicator which indicates the presence of the analyte in the fluid.
Claim 53
Dependent Claim 203 words
The method of claim 49, wherein the first detectable response of the first chemically sensitive element to permeation by said analyte is a first detectable dynamic aggregate response to permeation by said analyte, and wherein the second detectable response of the second chemically sensitive element to permeation by said analyte is a second detectable dynamic aggregate response to permeation by said analyte, wherein the step of comparing the first detectable measured response of the first element to said first detectable response to permeation by the analyte for the first element comprises comparing the first detectable measured response of the first element to said first detectable dynamic aggregate response to permeation by the analyte for the first element to generate a first indicator which indicates the presence of the analyte in the fluid, and wherein the step of comparing the second detectable measured response of the second element to said second detectable response to permeation by the analyte for the second element comprises comparing the second detectable measured response of the second element to said second detectable dynamic aggregate response to permeation by the analyte for the second element to generate a second indicator which indicates the presence of the analyte in the fluid.
Claim 54
Dependent Claim 23 words
The method of claim 49, further comprising the step of comparing said first indicator and said second indicator to create a response pattern.
Claim 55
Dependent Claim 27 words
The method of claim 49, further comprising the steps of: providing an information storage device coupled to said detector; and storing information in said information storage device.
Claim 56
Dependent Claim 51 words
The method of claim 49, wherein said first polymer in the first chemically sensitive element is the same as said first polymer in the second chemically sensitive element, and said second polymer in the first chemically sensitive element is the same as said second polymer in said second chemically sensitive element.
Claim 57
Dependent Claim 40 words
The method of claim 49, wherein concentration of the first polymer in said first blend of the first chemically sensitive element is different from the concentration of the first polymer in said second blend of the second chemically sensitive element.
Claim 58
Dependent Claim 175 words
The method of claim 49, wherein, during use, the first detectable dynamic aggregate response of the first element is created as the space occupied by said first blend of polymers in the first element and the composition of the first blend change in a nonconstant fashion as the first blend is permeated by the analyte where such change in space and composition of the first blend is different from change in space and composition of the first polymer and is different from change in space and composition of the second polymer, and the second detectable dynamic aggregate response of the second element is created as the space occupied by said second blend of polymers in the second element and the composition of the second blend change in a nonconstant fashion as the second blend is permeated by the analyte where such change in space and composition of the second blend is different from change in space and composition of the first polymer and is different from change in space and composition of the second polymer.
Claim 59
Dependent Claim 44 words
The method of claim 49, wherein the first detectable measured response, the first detectable dynamic aggregate response, the second detectable measured response and the second detectable dynamic aggregate response are each variations in electrical resistance, and wherein the detector is an electrical measuring apparatus.
Claim 60
Dependent Claim 18 words
The method of claim 49, wherein the first chemically sensitive element does not further comprise a conductive material.
Claim 61
Dependent Claim 18 words
The method of claim 49, wherein the second chemically sensitive element does not further comprise a conductive material.
Claim 62
Dependent Claim 28 words
The method of claim 51, further comprising the step of using said response pattern to indicate the absence of a substance different from said analyte in the fluid.
Claim 63
Dependent Claim 13 words
The method of claim 52, wherein the information storage device is a computer.

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