EP1141690A1 - Elements detecteurs bases sur des particules alignes - Google Patents

Elements detecteurs bases sur des particules alignes

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Publication number
EP1141690A1
EP1141690A1 EP99965062A EP99965062A EP1141690A1 EP 1141690 A1 EP1141690 A1 EP 1141690A1 EP 99965062 A EP99965062 A EP 99965062A EP 99965062 A EP99965062 A EP 99965062A EP 1141690 A1 EP1141690 A1 EP 1141690A1
Authority
EP
European Patent Office
Prior art keywords
analyte
fluid
detecting
aligned
sensor array
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.)
Ceased
Application number
EP99965062A
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German (de)
English (en)
Other versions
EP1141690A4 (fr
Inventor
Steven A. Sunshine
Beth C. Munoz
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.)
Smiths Detection Inc
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Smiths Detection Pasadena Inc
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Filing date
Publication date
Application filed by Smiths Detection Pasadena Inc filed Critical Smiths Detection Pasadena Inc
Publication of EP1141690A1 publication Critical patent/EP1141690A1/fr
Publication of EP1141690A4 publication Critical patent/EP1141690A4/fr
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0031—General constructional details of gas analysers, e.g. portable test equipment concerning the detector comprising two or more sensors, e.g. a sensor array

Definitions

  • Electronic noses are artificial sensory systems that are able to mimic chemical sensing.
  • electronic noses are arrays of sensors, which are able to generate electrical signals in response to analytes or vapors. For instance, it is possible to detect volatile materials by directly or indirectly measuring a response, such as a resistance, across each of the sensors in the array. Moreover, by providing different variables in each sensor of the array, such as the polymeric make-up of the sensors, it is possible to characterize various chemical materials according to the response of the array to that volatile material.
  • the electrical path length and resistance of a given gap are not constant, but change as the nonconductive region absorbs, adsorbs or imbibes an analyte.
  • the dynamic aggregate resistance provided by these gaps is, in part, a function of analyte permeation of the nonconductive regions.
  • the foregoing sensor is based on a conductive network in a nonconductive matrix. The swelling of the nonconductive matrix causes the conductive region to move apart changing the resistance of the sensor. The change in the resistance of the sensor can be correlated to the concentration of the vapor to be detected. The greater the resistance change for a given level of vapor, the lower the detection limit of the vapor being identified. It is thus advantageous to maximize the resistance change associated with the sensor elements.
  • SIN signal-to-noise ratio
  • the response of the sensors upon exposure to vapor is dependent on various factors.
  • One such factor is the percentage of connected paths that are broken.
  • the number of connected paths prior to exposure to a vapor is related to the percolation threshold.
  • the percolation threshold is defined as the particle volume fraction at which the conductivity of the resistor increases rapidly (i.e., an infinite number of conductive paths are formed and the lattice essentially transforms from an insulator to a conductor).
  • the percolation threshold is defined as the particle volume fraction at which the conductivity of the resistor increases rapidly (i.e., an infinite number of conductive paths are formed and the lattice essentially transforms from an insulator to a conductor).
  • At low volume loadings there are few connected paths; whereas at high volume loadings there are many connected paths.
  • Unfortunately there is concomitantly a high degree of noise at low volume loadings so that the signal to noise ratio is unsatisfactorily low.
  • the present invention provides a sensor array for detecting an analyte in a fluid, comprising: first and second sensors wherein the first sensor comprises a region of aligned conductive material; and wherein the sensor array is electrically connected to an electrical measuring apparatus.
  • the first and second sensors are first and second chemically sensitive resistors, each of the chemically sensitive resistors comprising: a plurality of alternating regions comprising a nonconductive region, such as an organic material, and an aligned conductive region.
  • the aligned conductive region comprises an aligned conductive material compositionally different from the nonconductive region.
  • each sensor such as a resistor, provides an electrical path through the nonconductive region and the aligned conductive region; and a first response such as an electrical resistance, when contacted with a first fluid comprising an analyte at a first concentration, and a second response when contacted with a second fluid comprising the analyte at a second different concentration.
  • the conductive region can be aligned using various processing techniques including, but are not limited to, exposure to an electric field, a thermal field, a magnetic field, an electromagnetic field, a photoelectric field, a light field, a mechanical field or combinations thereof.
  • aligned conductive region of the present invention can form various materials. Such materials include, but are not limited to, conductive materials, semi- conductive materials, magnetic materials, photoresponsive materials and combinations thereof.
  • the aligned conductive materials are preferably embedded in an organic matrix, such as a polymeric matrix.
  • the present invention relates to a system for detecting an analyte in a fluid, the system comprising: a sensor array comprising first and second sensors wherein the first sensor comprises a region of aligned conducting material.
  • the first and second sensors are first and second chemically sensitive resistors, each chemically sensitive resistor comprising a plurality of alternating regions comprising a nonconductive region and an aligned conductive region.
  • the aligned conductive region comprises an aligned conductive material compositionally different than the nonconductive region.
  • Each sensor such as a resistor, provides an electrical path through the nonconducting region and the aligned conductive region, a first response such as an electrical resistance, when contacted with a first fluid comprising an analyte at a first concentration and a second different response when contacted with a second fluid comprising the analyte at a second different concentration, wherein the difference between the first response and the second response of the first chemically sensitive resistor being different from the difference between the first response and the second response of the second chemically sensitive resistor under the same conditions; an electrical measuring device electrically connected to the sensor array; and a computer comprising a resident algorithm; wherein the electrical measuring device detecting the first and the second responses in each of the chemically sensitive resistors and the computer assembling the responses into a sensor array response profile.
  • a first response such as an electrical resistance
  • the present invention relates to a method for detecting the presence of an analyte in a fluid that can be either a liquid or a gas.
  • the method comprising: providing a sensor array comprising first and second sensors, wherein the first sensor comprises a region of aligned conductive material; and contacting the sensor array with the analyte to produce a response thereby detecting the presence of the analyte.
  • the first and second sensors are first and second chemically sensitive resistors, each comprising a plurality of alternating regions comprising a nonconductive region, such as an organic material, and an aligned conductive region.
  • the aligned conductive region comprises an aligned conductive material compositionally different from the nonconductive region.
  • each resistor provides an electrical path through the nonconducting region and the aligned conductive region, a first response such as an electrical resistance, when contacted with a first fluid comprising an analyte at a first concentration and a second different response when contacted with a second fluid comprising the analyte at a second different concentration.
  • Figure 1 shows a graph of a typical resistance versus volume loading for a non-aligned composite sensor.
  • Figure 2 shows a graph of resistance versus volume loading for a composite sensor where the particles have been aligned.
  • Figure 3 shows optical micrographs of unaligned sensor (left) and aligned sensor (right) Black Pearl 2000 (40 wt %) in 1,2-polybutadiene.
  • the present invention provides a sensor array for detecting an analyte in a fluid, comprising: first and second sensors wherein the first sensor comprises a region of aligned conducting material; and wherein the sensor array is connected to an electrical measuring apparatus.
  • the first and second sensors are first and second chemically sensitive resistors, each of the chemically sensitive resistors comprising: a plurality of alternating regions comprising a nonconductive region, such as a nonconductive organic material, and aligned conductive region, such as an aligned conductive material or particle.
  • the aligned conductive region is compositionally different from the nonconductive region.
  • the sensors such as resistors, provide an electrical path through the alternating regions comprising a nonconductive region, such as an organic material, and an aligned conductive region, a first response when contacted with a first fluid comprising an analyte at a first concentration, and a second response when contacted with a second fluid comprising the analyte at a second different concentration.
  • the response upon exposure to a vapor is dependent on various factors.
  • One such factor is the percentage of connected paths in the alternating regions that are broken.
  • the number of connected paths prior to exposure to a vapor is related to the percolation threshold.
  • the percolation threshold is defined as the volume fraction at which the conductivity of the resistor increases rapidly. At low volume loadings, there are very few connected paths. At high volume loadings, there are many connected paths.
  • composite sensors Upon exposure to vapors, composite sensors will exhibit a large change in resistance near their percolation threshold. Before the advent of the present invention, the noise level associated with such low volume loadings was prohibitively high. However, by aligning the conductive region, lower volume loadings can now be used. Moreover, by aligning the conductive region, the percolation threshold is easier to obtain at low volume loadings.
  • the sensors of the present invention have an aligned conductive region that results in reduced percolation thresholds.
  • Reduced percolation thresholds mean that a slight swelling of the composite sensor can result is a very large change in resistance. This is because the few conductive particles are all participating in the connected paths, and any discontinuity in the connectivity results in a large resistance change.
  • the alignment of the conductive region results in all of the particles participating in the connected electrical paths.
  • the alignment of the conductive region is effected through the application of various processing techniques.
  • polarization techniques can be used to align the conducting region. Suitable polarization techniques include, but are not limited to, exposure to an electric field, a thermal field, a magnetic field, an electromagnetic field, a photoelectric field, a light field, a mechanical field or combinations thereof.
  • the techniques employed to align the particles depends in part on the particle composition.
  • Suitable particles for use in the present invention include particles with a permanent magnetic dipole including, but not limited to, iron, nickel or cobalt require the use of a magnetic field for polarization to occur.
  • Particles such as carbon black, coke, C 6 o, and the like, TiO 2 , BaTiO 3 , In 2 O 3 , SnO 2 , Na x Pt 3 O 4 , conducting polymers, metals such as platinum, copper, gold, silver etc., polarize with application of an electric field.
  • the conductive material is a conducting polymer, or an insulating polymer with conductive fillers. Suitable conductive polymers are disclosed in U.S. Patent No.
  • the sensors taught therein comprise substituted polythiophenes.
  • One polymer is poly (3,3"-dihexyl-2-2":5',2"- terthiophene).
  • the conductive particle is carbon black.
  • the conductive material can be a particle, such as a gold nanoparticle, with a capping ligand shell. A preferred nanoparticle is disclosed in WO 99/27357, entitled “Materials, Method and Apparatus for Detection and Monitoring Chemical Species,” published June 3, 1999.
  • colloidal nanoparticles for use in accordance with the present invention are described in the literature (see, Templeton et al. J. Am. Chem. Soc. (1998) 120 : 1906-1911; Lee et al, Isr. J. Chem. (1997) 37: 213-223 (1997); Hostetler et al LANGMUIR (1998) 14: 17-30; Ingram et al, J. Am. Chem. Soc, (1997) 119 :9175-9178; Hostetler et al, J. Am Chem. Soc.( ⁇ 996) 118 :4212-4213; Henglein J. Phys. Chem. (1993) 97 :5457-5471; Zeiri, J. Phys.
  • Polarization processing such as magnetic field processing, involves exposure to various polarization mechanisms having different directions and optionally, different strengths.
  • exposure to a magnetic field can optionally be in one direction, such as in the x-, y- or z-direction; in two directions, such as x- and y-directions, x-and z-directions or y- and z-directions; or in three directions, such as x-, y- and z-directions.
  • the polarization processing is along the same axis as the vapor measurement. For instance, if the vapor measurement is along the z-direction, particle alignment will be along the z- direction.
  • the direction of expansion of the alternating regions is along the same axis as the vapor measurement.
  • the x-, y-, and z-axes have their traditional meaning, i.e., the x and y axes are in the plane of the sensor substrate and the z axis is perpendicular to the x and y origins.
  • sensor fabrication of the present invention can include other modes of polarization.
  • photosensitive conductive material will be exposed to optical radiation, such as visible, infrared or ultraviolet light.
  • Electrosensitive conductive material involves exposure to electric fields having different directions and different strengths.
  • enhancing the response of the sensor can be accomplished by confining the direction of expansion of the alternating regions to be along the axis of measurement or, preferably, along the axis of the particle alignment.
  • a polymer can have a 2% volume expansion on exposure to a certain vapor concentration. If this swelling can be isolated to one dimension, then the linear expansion can be as high as 8% causing a much larger change in resistance than would occur without confinement.
  • Aligning the conductive region e.g., material or particles, in a nonconducting matrix during deposition causes an increase in the number of conductive paths which in turn, results in a very low base resistance.
  • the formation of a conductive path is related to the percolation threshold of the material.
  • the percolation threshold varies from material to material depending on factors, such as particle size, shape and composition. Alignment of the conductive region will cause percolation to occur at a much lower volume loading. Thus, sensors containing aligned conductive regions will give a larger signal when exposed to a vapor compared to a sensor without aligned regions.
  • the nonconductive region such as an organic polymer
  • swells disruption of the particle chains occurs and a lowering in the conductivity or an increase in the resistance occurs.
  • the polymer desorbs, the particles return to their minimum energy state that corresponds to particle alignment.
  • Non-sensor alignment of particles are known.
  • U.S. Patent No. 4,177,228 issued to Prolss entitled “Method of Production of a Micro-Porous Membrane for Filtration Plants,” discloses the alignment of particles by various techniques.
  • U.S. Patent No. 5,742,223, issued to Simenddinger entitled
  • the present invention relates to conductive regions capable of alignment including, but not limited to, conductive, semi-conductive, magnetic and photoresponsive particles embedded in a nonconductive region, such as an organic matrix.
  • particles suitable for use while preferably spherical, are not limited by their shape and can even be in the form of flakes.
  • Suitable particulate materials that are magnetic include, but are not limited to, metals such as, nickel, cobalt and iron and their magnetic alloys.
  • Other suitable magnetic particles include, but are not limited to, oxides and intermetallic compounds as are known in the art.
  • Composite materials can also be used. These material include, but are not limited to, nickel coated with copper, or magnetically thermally conducting ceramics (see, U.S. Patent No.
  • Additional magnetic particles include, but are not limited to, alloys containing nickel, iron, cobalt and ferrites. Also conductive surface coatings can be used. Precious metal coatings include, but are not limited to, silver, gold and precious metal alloys (see, U.S. Patent Nos. 4,923,739 and 4,737,112 incorporated herein by reference).
  • the conductive region can be a substrate, such as a particle, coated with metal.
  • Suitable substrates include, but are not limited to, glass, silicon, quartz, ceramic or combination thereof.
  • the present invention has advantages over current sensor technology.
  • One advantage is the use of lower concentrations of particles, which leads to ease of dispersion.
  • the rate of particle sedimentation is proportional to the number of particles in the dispersion.
  • Another advantage is the increased stability of the sensors of the present invention, especially when the polymer matrix is crosslinked (i.e., the polymer molecules are interconnected forming a 3-dimensional network).
  • a third advantage is an increase in the sensitivity of the sensors leading to lower limits of detection (i.e., increased dynamic range). The latter advantage is due to the much higher signal-to-noise ratio given by the sensors having an aligned conductive region.
  • the major advantage of this invention over the sensors of the prior art is that the signal-to-noise ratio is much higher. Because of the increase in the signal-to-noise ratio, the limit of detection increases (i.e., a smaller concentration of analyte is capable of detection). In addition, the response time is faster. A faster response time is critical in applications such as quality control where the analyte may be on a conveyor belt with a very short time for detection. In general, sensors with greater response times are better than sensor with lower response times.
  • Various sensor responses of the present invention include, but are not limited to, resistance, capacitance, inductance, impedance, and combinations thereof.
  • the nonconductive region of the sensors comprise an organic material. In certain preferred aspects, the organic material is an organic polymer. Organic polymers suitable for use in the present invention include, but are not limited to, those set forth in Table 1. TABLE 1
  • the sensors of the present invention can be fabricated by many techniques including, but not limited to, solution casting, suspension casting, matrix assisted pulsed laser evaporation (MAPLE), MAPLE-Direct Write (MAPLE-DW) (see, R. Andrew McGill, et al, IEEE Transactions on Ultrasonics, Ferroelectrics, and Frequency Control 45: 1370-1380 (1998), and mechanical mixing.
  • solution casting routes are advantageous because they provide homogeneous structures and are easy to process.
  • resistor elements can be easily fabricated by spin, spray or dip coating. Since all elements of the resistor must be soluble, solution casting routes can be somewhat limited in their applicability.
  • the resistor is deposited as a surface layer on a solid matrix that provides means for supporting the leads.
  • the solid matrix is a chemically inert, nonconductive substrate, such as a glass or ceramic.
  • Sensor arrays of the present invention are particularly well-suited to scaled up production by being fabricated using integrated circuit (IC) design technologies.
  • the chemiresistors can easily be integrated onto the front end of a simple amplifier interfaced to an A/D converter to efficiently feed the data stream directly into a neural network software or hardware analysis section.
  • Micro-fabrication techniques can integrate the chemiresistors directly onto a micro-chip that contains the circuitry for analogue signal conditioning/processing and then data analysis. This provides for the production of millions of incrementally different sensor elements in a single manufacturing step using ink-jet technology. Controlled compositional gradients in the chemiresistor elements of a sensor array can be induced in a method analogous to how a color ink-jet printer deposits and mixes multiple colors.
  • a sensor array of a million distinct elements only requires a 1 cm x 1 cm sized chip employing lithography at the 10 ⁇ m feature level, which is within the capacity of conventional commercial processing and deposition methods. This technology permits the production of sensitive, small-sized, stand-alone chemical sensors.
  • Suitable polarization processing includes, but is not limited to, magnetic field processing which involves exposure to magnetic fields, photolytic field processing which involves exposure to optical radiation, electric field processing which involves exposure to electric fields, and combinations thereof.
  • photolytic field processing light sensitive material can be exposed to optical radiation, such as visible, infrared, or ultraviolet light (see, U.S. Patent No. 4,737,112). All of the foregoing polarization processing techniques can have different axes direction and different strengths.
  • Preferred sensor arrays have a predetermined inter-sensor variation in the structure or composition of the nonconductive regions (e.g., the nonconductive organic material).
  • the variation can be quantitative and/or qualitative.
  • the concentration of the nonconductive organic material in the blend can be varied across sensors.
  • a variety of different alignment techniques are possible within the sensor array.
  • the polarization processing techniques e.g., magnetic and electric fields
  • An electronic nose for detecting an analyte in a fluid is fabricated by electrically coupling the sensor leads of an array of compositionally different sensors to an electrical measuring device.
  • the device measures changes in resistivity at each sensor of the array, preferably simultaneously and preferably over time.
  • the device includes signal processing means and is used in conjunction with a computer and data structure for comparing a given response profile to a structure-response profile database for qualitative and quantitative analysis.
  • the present invention relates to a system for detecting an analyte in a fluid, comprising: a sensor array comprising first and second sensors wherein the first sensor comprises a region of aligned conducting material.
  • the first and second sensors are first and second chemically sensitive resistors, each chemically sensitive resistor comprising a plurality of alternating regions comprising a nonconductive region, such as a nonconductive organic material, and an aligned conductive region, such as an aligned conductive material compositionally different than the nonconductive region.
  • Each resistor provides an electrical path through the alternating nonconducting region and the aligned conductive regions, a first response such as an electrical resistance, when contacted with a first fluid comprising an analyte at a first concentration and a second different response when contacted with a second fluid comprising the analyte at a second different concentration, the difference between the first response and the second response of the first sensor being different from the difference between the first response and the second response of the second sensor under the same conditions; an electrical measuring device electrically connected to the sensor array; and a computer comprising a resident algorithm; the electrical measuring device detecting the first and said second responses in each of the sensors and the computer assembling the responses into a sensor array response profile.
  • a first response such as an electrical resistance
  • such sensor arrays and electronic noses of the present invention comprise at least ten, usually at least 100, and often at least 1000 different sensors, though with mass deposition fabrication techniques described herein or otherwise known in the art, arrays of on the order of at least 10 6 sensors are readily produced.
  • each resistor provides a first electrical resistance between its conductive leads when the resistor is contacted with a first fluid comprising an analyte at a first concentration, and a second electrical resistance between its conductive leads when the resistor is contacted with a second fluid comprising the same analyte at a second different concentration.
  • the fluids can be liquid or gaseous in nature.
  • the first and second fluids may reflect samples from two different environments, a change in the concentration of an analyte in a fluid sampled at two time points, a sample and a negative control, etc.
  • the sensor array necessarily comprises sensors that respond differently to a change in an analyte concentration, i.e., the difference between the first and second electrical resistance of one sensor is different from the difference between the first and second electrical resistance of another sensor.
  • the sensor array can comprise redundant sensors that can be advantageous for maximizing the signal and thus reducing the noise in the signal.
  • analyte detection systems comprising sensor arrays, an electrical measuring device for detecting resistance across each chemiresistor, a computer, a data structure of sensor array response profiles, and a comparison algorithm are provided.
  • the electrical measuring device is an integrated circuit comprising neural network-based hardware and a digital-analog converter (DAC) multiplexed to each sensor, or a plurality of DACs, each connected to different sensor(s).
  • DAC digital-analog converter
  • a wide variety of analytes and fluids may be analyzed by the disclosed sensors, arrays and noses so long as the subject analyte is capable of generating a differential response across a plurality of sensors of the array.
  • Analyte applications include broad ranges of chemical classes including, but not limited to, organics such as alkanes, alkenes, alkynes, dienes, alicyclic hydrocarbons, arenes, heterocyclics, alcohols, ethers, ketones, aldehydes, carbonyls, carbanions, polynuclear aromatics and derivatives of such organics, e.g., halide derivatives, etc., microorganism off-gases, fungi, bacteria, microbes, viruses, metabolites, biomolecules such as sugars, isoprenes and isoprenoids, fatty acids and derivatives, etc.
  • organics such as alkanes, alkenes, alkynes, dienes, alicyclic hydrocarbons, arenes, heterocyclics, alcohols, ethers, ketones, aldehydes, carbonyls, carbanions, polynuclear aromatics and derivatives of such organics, e.g., halide derivative
  • commercial applications of the sensors, arrays and noses include environmental toxicology and remediation, biomedicine, materials quality control, food and agricultural products monitoring. Further applications include, but are not limited to: heavy industrial manufacturing (automotive, aircraft, etc.), such as ambient air monitoring, worker protection, emissions control, and product quality testing; oil/gas petrochemical applications, such as combustible gas detection, H 2 S monitoring, and hazardous leak detection and identification; emergency response and law enforcement applications, such as illegal substance detection and identification, arson investigation, hazardous spill identification, enclosed space surveying, and explosives detection; utility and power applications, such as emissions monitoring and transformer fault detection; food/beverage/agriculture applications, such as freshness detection, fruit ripening control, fermentation process monitoring and control, flavor composition and identification, product quality and identification, and refrigerant and fumigant detection; cosmetic/perfume applications, such as fragrance formulation, product quality testing, and patent protection fingerprinting; chemical/plastics/pharmaceuticals applications, such as fugitive emission identification, leak detection, solvent recovery effectiveness, perimeter monitoring,
  • the present invention relates to a method for detecting the presence of an analyte in a fluid comprising: providing a sensor array comprising first and second sensors, wherein the first sensor comprises a region of aligned conductive material; and contacting the sensor array with the analyte to produce a response thereby detecting the presence of the analyte.
  • the first and second sensors are first and second chemically sensitive resistors each comprising a plurality of alternating nonconductive regions, such as nonconductive organic material, and aligned conductive regions, such as an aligned conductive material compositionally different than the nonconductive region, each resistor providing an electrical path through the nonconducting region and aligned conductive region, a first response such as an electrical resistance, when contacted with a first fluid comprising an analyte at a first concentration and a second different response when contacted with a second fluid comprising the analyte at a second different concentration.
  • first and second chemically sensitive resistors each comprising a plurality of alternating nonconductive regions, such as nonconductive organic material, and aligned conductive regions, such as an aligned conductive material compositionally different than the nonconductive region, each resistor providing an electrical path through the nonconducting region and aligned conductive region, a first response such as an electrical resistance, when contacted with a first fluid comprising an analyte at a first
  • the general method for using the disclosed sensor arrays and electronic noses for detecting the presence of an analyte in a fluid preferably involves resistively sensing the presence of an analyte in a fluid with a chemical sensor comprising first and second conductive leads electrically coupled to and separated by a chemically sensitive resistor as described above by measuring a first resistance between the conductive leads when the resistor is contacted with a first fluid comprising an analyte at a first concentration and a second different resistance when the resistor is contacted with a second fluid comprising the analyte at a second different concentration.
  • the methods and systems of the present invention can be used for monitoring medical conditions and disease processes.
  • WO 98/29563 published July 9, 1998, and incorporated herein by reference, discloses a method for monitoring conditions in a patient wherein a sample is obtained from a patient over a period of time. The samples are then flowed over a gas sensor and a response is measured. Thereafter, the response is correlated with known responses for known conditions.
  • the conditions include, but are not limited to, the progression and or regression of a disease state, bacterial infections, viral, fungal or parasitic infections, the effectiveness of a course of treatment and the progress of a healing process.
  • the methods and systems of the present invention can be used for monitoring medical conditions in a respiring subject.
  • WO 98/39470 discloses a method for detecting the occurrence of a condition in a respiring subject.
  • the method comprises introducing emitted respiratory gases to a gas sensing device, detecting certain species present in the gas and correlating the presence of the species with certain conditions.
  • a wide variety of conditions can be ascertained using this aspect of the present invention. These conditions include, but are not limited to, halitosis, ketosis, yeast infections, gastrointestinal infections, diabetes, alcohol, phenylketonuria, pneumonia, and lung infections.
  • Those of skill in the art will know of other conditions and diseases amenable to the methods and systems of the present invention.
  • the sensor arrays, systems and methods of the present invention comprise: first and second sensors wherein the first sensor comprises a region of aligned conducting material.
  • the second sensor can also comprise a region of aligned conductive material.
  • the second sensor is a different sensor type.
  • Suitable sensor types include, but are not limited to, a surface acoustic wave (SAW) sensor; a quartz microbalance sensor; a conductive composite; a metal oxide gas sensor, an organic gas sensor; an infrared sensor; a sintered metal oxide sensor; a phthalocyanine sensor; an electrochemical cell; a conducting polymer sensor; a catalytic gas sensor; an organic semiconducting gas sensor; a solid electrolyte gas sensor; a temperature sensor; a humidity sensor; fiber optic micromirrors; dye impregnated polymeric coatings on optical fibers and a Langmuir-Blodgett film sensor.
  • SAW surface acoustic wave
  • quartz microbalance sensor a quartz microbalance sensor
  • a conductive composite a metal oxide gas sensor, an organic gas sensor; an infrared sensor; a sintered metal oxide sensor; a phthalocyanine sensor
  • an electrochemical cell a conducting polymer sensor
  • a catalytic gas sensor an
  • the sensors of the present invention comprise a chiral center.
  • European Patent Application No. 0 794 428 published September 10, 1997, describes sensors capable of distinguishing between enantiomers.
  • the sensor comprise a pair of spaced apart contacts and a conducting polymer material spanning the gap.
  • the polymer has chiral sites in the polymer material formed by incorporating optically active counter ions such as camphor sulfonic acid.
  • WO 99/40423 published August 12, 1999, discloses sensor arrays of that are capable of distinguishing or differentiating between chiral compounds. That publication relates to a device for detecting the presence or absence of an analyte in a fluid, the device comprises a sensor, the sensor comprising a chiral region.
  • the sensor comprises a conductive region and a nonconductive region, wherein at least one of the conductive and nonconductive regions is chiral, and wherein the analyte generates a differential response across the sensor.
  • the sensor arrays of the present invention comprise sensors disclosed in WO 99/00663, published January 7, 1999.
  • a combinatorial approach for preparing arrays of chemically sensitive polymer- based sensors are capable of detecting the presence of a chemical analyte in a fluid contact therewith.
  • the described methods and devices comprise combining varying ratios of at least first and second organic materials which, when combined, form a polymer or polymer blend that is capable of absorbing a chemical analyte, thereby providing a detectable response.
  • the detectable response of the sensors prepared by this method is not linearly related to the mole fraction of at least one of the polymer-based components of the sensor.
  • This Example illustrates the difference in percolation threshold in non- aligned sensors versus aligned sensors.
  • the percolation threshold is defined as the particle volume fraction at which the conductivity of the resistor increases rapidly i.e., an infinite number of conductive paths are formed and the lattice essentially transforms from an insulator to a conductor.
  • Figure 1 illustrates a typical resistance versus volume loading for a non- aligned composite sensor, where the percolation threshold occurs at about 20 volume percent filler.
  • Figure 2 shows a graph of resistance versus volume loading for a composite sensor where the particles have been aligned. The percolation threshold occurs at about 5 volume percent filler.
  • This Example illustrates a sensor array that was fabricated by depositing Black Pearl 2000 (40 wt %) dispersed in 1,2-polybutadiene in the presence of an electric field.
  • the conductive particles respond to the field by migrating to minimum energy states, which in this case corresponds to chain-like structures aligned parallel to the electric field. As the solvent evaporates the chains are locked in place.
  • Figure 3 illustrates the particle alignment after using 48 volts across the sensor electrodes during the deposition process.

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  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
  • Investigating Or Analysing Biological Materials (AREA)

Abstract

L'invention concerne un ensemble capteur permettant de détecter un analyte dans un fluide, comprenant un premier et un second détecteur constitué chacun de résistances chimiquement sensibles. Le premier détecteur comprend une zone de matériau conducteur aligné; ou alors chaque détecteur comprend des régions alternées de zones non conductrices et de zones conductrices alignées alternées. Chaque résistance présente un trajetlectrique traversant les deux zones, non conductrice et conductrice alignée. Chaque détecteur présente une résistance électrique différente, lors du contact avec des fluides échantillons de différentes teneurs d'analyte, par le biais de l'agencement de contrôle qui relie électriquement les détecteurs à un appareil électrique de mesure. Le matériau particulaire conducteur aligné est aligné par l'exposition à un champ électrique, magnétique, optique, photoélectrique, électromagnétique ou mécanique, qui sert à améliorer le rapport signal bruit des détecteurs de vapeur, ce qui permet des seuils de détection inférieurs pour les vapeurs mesurées. De tels seuils de détection inférieurs permettent d'identifier des teneurs plus faibles de matériaux dangereux et présentent des avantages dans des applications médicales telles que la détection d'états pathologiques chez un patient.
EP99965062A 1998-12-01 1999-11-30 Elements detecteurs bases sur des particules alignes Ceased EP1141690A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US20199998A 1998-12-01 1998-12-01
US201999 1998-12-01
PCT/US1999/028282 WO2000033062A1 (fr) 1998-12-01 1999-11-30 Elements detecteurs bases sur des particules alignes

Publications (2)

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EP1141690A1 true EP1141690A1 (fr) 2001-10-10
EP1141690A4 EP1141690A4 (fr) 2002-08-07

Family

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Country Link
EP (1) EP1141690A4 (fr)
AU (1) AU3105900A (fr)
WO (1) WO2000033062A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7113069B1 (en) 1999-11-30 2006-09-26 Smiths Detection Inc. Aligned particle based sensor elements
TW496775B (en) * 1999-03-15 2002-08-01 Aviva Bioscience Corp Individually addressable micro-electromagnetic unit array chips
CN1185492C (zh) 1999-03-15 2005-01-19 清华大学 可单点选通式微电磁单元阵列芯片、电磁生物芯片及应用
DE60026309T2 (de) 1999-05-10 2006-12-14 California Institute Of Technology, Pasadena Verwendung eines räumlich-zeitlichen reaktionsverhaltens in sensor-arrays zur detektion von analyten in fluiden
US6890715B1 (en) 1999-08-18 2005-05-10 The California Institute Of Technology Sensors of conducting and insulating composites
JP2004510953A (ja) * 1999-12-30 2004-04-08 キャボット　コーポレイション 改良された性質を有するセンサー
FR2820824B1 (fr) * 2001-02-12 2004-06-04 Total Raffinage Distribution Dispositif de mesure de l'efficacite d'une huile lubrifiante et ses applications
DE60144014D1 (de) 2001-07-19 2011-03-24 Max Planck Gesellschaft Chemische Sensoren aus Nanopartikel-Dendrimer-Komposit-Materialen
WO2008088867A1 (fr) 2007-01-19 2008-07-24 Cantimer Incorporated Capteur à micro-porte-à-faux piézoélectrique et composition correspondante
US9803236B2 (en) 2010-08-06 2017-10-31 Tsinghua University Microarray-based assay integrated with particles for analyzing molecular interactions
CN103760355B (zh) 2013-12-05 2015-09-16 博奥生物集团有限公司 微阵列芯片检测中核苷酸序列的颗粒标记方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4581204A (en) * 1983-06-02 1986-04-08 Siemens Aktiengesellschaft Thin film gas sensor
EP0306183A2 (fr) * 1987-08-31 1989-03-08 Junkosha Co. Ltd. Capteur de fuite d'huile
US5238729A (en) * 1991-04-05 1993-08-24 Minnesota Mining And Manufacturing Company Sensors based on nanosstructured composite films
WO1997023777A1 (fr) * 1995-12-22 1997-07-03 Capteur Sensors & Analysers Ltd. Detecteurs de gaz a electrodes multiples et leurs procedes de fabrication et d'utilisation
DE19718584C1 (de) * 1997-05-05 1998-11-19 Fraunhofer Ges Forschung Sensor zur Detektion von oxidierenden und/oder reduzierenden Gasen oder Gasgemischen

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4198851A (en) * 1978-05-22 1980-04-22 University Of Utah Method and structure for detecting the concentration of oxygen in a substance
CA1108234A (fr) * 1978-08-02 1981-09-01 George A. Volgyesi Mesure de la concentration des gaz anesthesiques
US4644101A (en) * 1985-12-11 1987-02-17 At&T Bell Laboratories Pressure-responsive position sensor
US4737112A (en) * 1986-09-05 1988-04-12 American Telephone And Telegraph Company, At&T Bell Laboratories Anisotropically conductive composite medium
US4923739A (en) * 1987-07-30 1990-05-08 American Telephone And Telegraph Company Composite electrical interconnection medium comprising a conductive network, and article, assembly, and method
US5512882A (en) * 1991-08-07 1996-04-30 Transducer Research, Inc. Chemical sensing apparatus and methods
US5571401A (en) * 1995-03-27 1996-11-05 California Institute Of Technology Sensor arrays for detecting analytes in fluids
US5742223A (en) * 1995-12-07 1998-04-21 Raychem Corporation Laminar non-linear device with magnetically aligned particles
US5942674A (en) * 1997-08-04 1999-08-24 Ford Global Technologies, Inc. Method for detecting oxygen partial pressure using a phase-transformation sensor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4581204A (en) * 1983-06-02 1986-04-08 Siemens Aktiengesellschaft Thin film gas sensor
EP0306183A2 (fr) * 1987-08-31 1989-03-08 Junkosha Co. Ltd. Capteur de fuite d'huile
US5238729A (en) * 1991-04-05 1993-08-24 Minnesota Mining And Manufacturing Company Sensors based on nanosstructured composite films
WO1997023777A1 (fr) * 1995-12-22 1997-07-03 Capteur Sensors & Analysers Ltd. Detecteurs de gaz a electrodes multiples et leurs procedes de fabrication et d'utilisation
DE19718584C1 (de) * 1997-05-05 1998-11-19 Fraunhofer Ges Forschung Sensor zur Detektion von oxidierenden und/oder reduzierenden Gasen oder Gasgemischen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO0033062A1 *

Also Published As

Publication number Publication date
AU3105900A (en) 2000-06-19
WO2000033062A9 (fr) 2000-12-07
EP1141690A4 (fr) 2002-08-07
WO2000033062A1 (fr) 2000-06-08
WO2000033062A8 (fr) 2000-09-21

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