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
  • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
  • G01N33/483—Physical analysis of biological material
  • G01N33/497—Physical analysis of biological material of gaseous biological material, e.g. breath
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
  • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
  • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
  • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
  • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
  • G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
• • 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
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N2291/00—Indexing codes associated with group G01N29/00
  • G01N2291/02—Indexing codes associated with the analysed material
  • G01N2291/028—Material parameters
  • G01N2291/02863—Electric or magnetic parameters

Definitions

• This invention relates generally to sensor systems for detecting analytes in fluids and, more particularly, to sensor systems of this kind that incorporate sensors having responses, such as electrical resistances, that vary according to the presence and concentration of analytes, and to methods of using such sensor systems.
• sensors that act as analogs of the mammalian olfactory system (see, Lundstrom et al. (1991) Nature 352:47-50; Shurmer and Gardner (1992) Sens. Act. B 8:1-11).
• This system is thought to utilize probabilistic repertoires of many different receptors to recognize a single odorant (see, Reed (1992) Neuron 8:205-209; Lancet and Ben-Airie (1993) Curr. Biol. 3:668-674).
• Metal oxide sensors such as SnO 2 films that have been coated with various catalysts are used primarily to detect gas leaks, e.g., carbon monoxide (CO).
• Gas leak detection is a specific chemical sensing application in which the existing technology is well- established.
• the current technology in this area is problematic in that metal oxide sensors work only at high power, i.e., they must be plugged into a conventional ac power source. This is because the metal oxide element must be heated for the chemical detection to work. The heated element literally burns methane, propane, CO, etc., to carbon dioxide. Oxygen for the combustion reaction is actually supplied by the metal oxide itself, and it is the absence of oxygen that sets off an electrical current in the metal oxide element thereby detecting the presence of the gas. Different gases are detected by metal oxide sensors based upon the addition of certain catalysts.
• Existing metal oxide sensors are single-channel devices that collect information from a single sensor and that are thus designed to trigger only when the gas, e.g., CO, is present.
• the devices can be prone to false alarms, and in many cases consumers disable the devices because of this annoyance.
• a sensor is needed with a lower false alarm rate to overcome the problematic user error. This can be accomplished by adding an additional sensor to CO detectors, which provides information that the odor is not CO, thereby lowering the occurrence of false alarms and providing significant product improvement.
• profiling a chemical environment rather than simply indicating the presence or absence of a gas leak, has far more utility in many applications, e.g., fire- fighting.
• a hand-held or chip-based product that could identify the chemicals given off by fires could be used by fire fighters to indicate the particular fire retardants that would work best and the protective gear to wear, etc.
• Such 'smart' environmental profilers would be suitable for integration into standard room monitoring devices, e.g., thermostats, smoke detectors, etc., and thereby represent a major market opportunity.
• Electron capture chemical detectors are another example of a well-known chemical sensor technology.
• the technology is based upon a chemical principle called electron capture, in which electrons are emitted from a filament and captured only by molecules that readily add an electron. These molecules, having added an electron, become negatively charged and can be diverted towards a charged electric plate where they can be detected. A limited number of molecules exhibit this characteristic.
• These include primarily freons and are the basis for hand-held refrigerant detectors. Freons are responsible for ozone depletion and are considered an environmental hazard.
• a small chip-based sensor could be useful for detecting freon leaks and could be mounted on refrigeration units for early detection of freon leaks, thus providing near instantaneous detection and mitigation of environmental damage.
• GC gas chromatography
• MS mass spectroscopy
• Such elements should be simply prepared and are readily modified chemically to respond to a broad range of analytes.
• these sensors should yield a rapid, low-power, dc electrical signal in response to the fluid of interest, and their signals should be readily integrated with sof vare- or hardware-based neural networks for purposes of analyte identification.
• an analyte detection system comprising the sensor, an information storage and processing device, and a fluid delivery appliance.
• the fluid deliveiy appliance should be operatively associated with the sensor for delivery of the analyte.
• No known products, technologies or approaches are capable of generating hand-held general odor detectors.
• a further object of the invention is to provide a chip-based odor detection system.
• no known competitive technologies or approaches to odor detection are chip-based. Integration of the sensor, the information storage and processing device, and the fluid delivery system onto a single substrate would provide a significant advancement over existing technology.
• the invention provides methods, apparatus and expert systems for detecting analytes in fluids.
• the apparatus include a chemical sensor comprising first and second conductive elements (e.g., electrical leads) electrically coupled to 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).
• the electrical path between the first and second conductive elements is transverse to (i.e., passes through) said plurality of alternating nonconductive and conductive regions.
• 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.
• an information storage and processing device is operatively connected with the device, for comparing a response from the detector with a stored ideal response, to detect the presence of the analyte.
• the information storage and processing device stores ideal responses for two analytes, and the device detects the presence of each analyte.
• an integrated system for detecting an analyte in a fluid includes a sensing device that comprises a substrate and an array of sensors made from a first organic material, having a response to permeation by an analyte, and further comprising a detector operatively associated with the sensor.
• the sensing device of this embodiment contains an information storage and processing device incorporated in the substrate, for measuring the response profile from the detector. The response profile is compared to the response profile of a stored ideal response for the analyte, to detect the presence of the analyte.
• the system of this embodiment also contains a fluid delivery mechanism in the substrate, for delivering fluid to the array of sensors.
• the present invention provides a method for determining the presence of an analyte, comprising: contacting a sensor to produce a response to the presence of vapor in contact therewith; measuring the sensor's response to the vapor using a detector; andcomparing the sensor's measured response with a stored response to determine the presence of the analyte.
• the sensor is an array of sensors comprising at least one smart sensor.
• Another preferred method includes the steps of sensing first and second sensors, and detecting the presence of an analyte using a detector operatively associated with the sensors.
• the method also delivers fluid to the sensors and measures the response of the sensors using the detector. Further, the response is compared to a stored ideal response for the analyte, to determine the presence of the analyte.
• the fluid measured can be a gaseous fluid, a liquid, or a fluid extracted from a solid. Methods of fluid delivery for each embodiment are accordingly provided.
• FIG. 1 depicts an array of 16 sensors for use in sensing the presence and concentration of unknown analytes, wherein each sensor incorporates a unique formulation of conducting and nonconducting materials.
• FIG. 1 A is an enlarged view of one sensor of the sensor array of FIG. 1.
• FIG. 2 is a schematic view of one sensor of the sensor array of FIG. 1, depicting the sensor's interdigitized leads and overlaying composite resistive material.
• FIG. 2 A depicts a typical response signal produced by the sensor of FIG. 2 when exposed to a particular analyte.
• FIG. 3 depicts an array of eight sensors like that of FIG. 2, along with a set of response signals produced by the sensors when exposed to a particular analyte.
• FIG. 4 is a schematic view of several different sets of response signals produced by the sensor array of FIG. 3 when exposed to several known analytes.
• FIG. 5 is a simplified block diagram of the sensor system of the invention.
• FIG. 6 depicts a cyclic voltammogram of a poly(pyrrole)-coated platinum electrode.
• the electrolyte was 0.10 M [(C 4 H ) 4 N] + [ClO 4 ] ⁇ in acetonitrile, with a scan rate of 0.10 V s "1 .
• FIG. 7A shows the optical spectrum of a spin coated poly(pyrrole) film that had been washed with methanol to remove excess pyrrole and reduced phosphomolybdic acid.
• FIG. 7B shows the optical spectrum of a spin-coated poly(pyrrole) film on indium-tin-oxide after ten potential cycles between +0.70 and -1.00 V vs. SCE in 0.10 M [(C 4 H 9 ) N] + [ClO 4 ] " in acetonitrile at a scan rate of 0.10 V -s "1 .
• the spectra were obtained in 0.10 M KC1 - H 2 O.
• FIG. 8 A is a schematic representation of a sensor array showing an enlargement of one of the modified ceramic capacitors used as sensing elements.
• the response patterns generated by the sensor array described in Table 3 are displayed for: FIG. 8B acetone; FIG. 8C benzene; and FIG. 8D ethanol.
• FIGS. 9A-D schematically depicts a principle component analysis of autoscaled data from individual sensors containing different plasticizers. The numbers in the upper right corner of each depicted square refer to the different sensor elements described in Table 3.
• FIGS. 10A-B depict a principle component analysis of data obtained from all of the sensors of Table 3. Conditions and symbols are identical to FIGS. 9A-D.
• FIG. 9A-D is a schematic representation of a sensor array showing an enlargement of one of the modified ceramic capacitors used as sensing elements.
• the response patterns generated by the sensor array described in Table 3 are displayed for: FIG. 8B acetone; FIG. 8C benzene; and FIG. 8D ethanol.
• FIG. 10A shows data represented in the first three principle components pel, pc2 and pc3, while FIG. 10B shows the data when represented in pel, pc2, and pc4.
• FIG. 10B shows the data when represented in pel, pc2, and pc4.
• a higher degree of discrimination between some solvents could be obtained by considering the fourth principle component as illustrated by larger separations between chloroform, tetrahydrofuran, and isopropyl alcohol in FIG. 10B.
• FIG. 12 is a plot of the resistance response of a poly(N- vinylpyrrolidone):carbon black (20 w/w% carbon black) sensor element to methanol, acetone, and benzene.
• Each trace is normalized by the resistance of the sensor element (approx. 125 ohms) before each exposure.
• FIG. 13 is a schematic representation of the first three principal components for the response of a carbon-black based sensor array with ten elements.
• the non-conductive components of the carbon-black composites used are listed in Table 3, and the resistors were 20 w/w% carbon black.
• FIG. 14A is a perspective view of a tabletop device, or box-type sensor, for detecting odors, in accordance with the invention.
• FIG. 14B is a perspective view of a hand-held device for detecting odors, in accordance with the invention.
• FIG. 14C is a perspective view of an integrated chip device for detecting odors, in accordance with the invention.
• FIG. 15 is a schematic view of a sensor-based fluid detection device used as an automotive oil change monitor.
• FIG. 16 is a perspective view of a sensor-based fluid detection device used as an automotive antifreeze monitor.
• FIG. 17 is a perspective view of a sensor-based fluid detection device used to monitor and detect emissions in the intake system of an automobile's internal combustion engine.
• FIG. 18 is a schematic view of a sensor-based fluid detection device used to monitor and detect emissions in the exhaust system of an automobile's internal combustion engine.
• FIG. 19 is a perspective view of a sensor-based fluid detection system used to monitor and detect emissions from cooking and heating food.
• FIG. 20 is a perspective view of a hand-held sensor-based fluid detection system for use in monitoring and detecting personal body odors.
• FIG. 21 is a perspective view of a hand-held sensor-based fluid detection system for use in soil analysis.
• FIG. 22 is a perspective view of a sensor-based fluid detection system for monitoring the environmental conditions within an office.
• FIG. 23 is a perspective view of a sensor-based fluid detection system that is part of a modern HNAC system, for use in controlling environmental conditions in homes and buildings.
• FIG. 24 is a perspective view of a hand-held sensor-based fluid detection system used to detecting leaks in an industrial manufacturing plant.
• FIG. 25 is a perspective view of a hand-held sensor-based fluid detection system used to detect and identify hazardous materials that have been accidentally spilled.
• FIG. 26 is a perspective view of a hand-held sensor-based fluid detection system used to detect and identify hazardous materials present in landfills and the like.
• FIG. 27 is a perspective view of a hand-held sensor-based fluid detection system used to detect the presence of explosives, e.g., land mines, and other hazardous materials.
• FIG. 28 is a perspective view of a sensor-based fluid detection system used to monitor the condition of food being processed in a food processing plant.
• FIG. 29 is a perspective view of a hand-held sensor-based fluid detection system used to monitor the condition of food being prepared in a commercial establishment.
• FIG. 30 is a perspective view of a sensor-based fluid detection system used to the monitor the condition of beverages being produced in a bottling plant.
• FIG. 31 is a perspective view of a hand-held sensor-based fluid detection system used by a law enforcement officer to analyze the breath of a motorist following a motor vehicle accident.
• FIG. 32 is a perspective view of a hand-held sensor-based fluid detection system used by a medical practitioner to the monitor a patient's breath, as part of a diagnosis of the patient's condition.
• FIG. 33 is a perspective view of a hand-held sensor-based fluid detection system used by a emergency medical technician to detect the presence of stomach gas during an intubation procedure.
• FIG. 34 is a perspective view of a hand-held sensor-based fluid detection system integrated into a catheter, for use in monitoring a gases present in certain body cavities.
• the array comprises a plurality of compositionally different chemical sensors, each sensor comprising at least first and second conductive leads electrically coupled to and separated by a chemically sensitive resistor.
• the leads may be any convenient conductive material, usually a metal, and may be interdigitized to maximize signal-to-noise strength (see FIG. 1 A).
• the resistor comprises a plurality of alternating nonconductive and conductive regions transverse to the electrical path between the conductive leads.
• the resistors are fabricated by blending a conductive material with a nonconductive organic polymer such that the electrically conductive path between the leads coupled to the resistor is interrupted by gaps of non-conductive organic polymer material.
• the matrix regions separating the particles provide the gaps.
• the nonconductive gaps range in path length from about 10 to 1,000 angstroms, usually on the order of 100 angstroms providing individual resistance of about 10 to 1,000 megaohms, usually on the order of 100 megaohms, across each gap.
• the path length and resistance of a given gap is not constant but rather is believed to change as the nonconductive organic polymer of the region absorbs, adsorbs or imbibes an analyte. Accordingly the dynamic aggregate resistance provided by these gaps in a given resistor is a function of analyte permeation of the nonconductive regions.
• the conductive material may also contribute to the dynamic aggregate resistance as a function of analyte permeation (e.g., when the conductive material is a conductive organic polymer such as polypyrrole).
• FIG. 2 depicts a single sensor 21 having a resistance that varies according to the amount of analyte permeation into the composite polymer material overlaying its interdigitized leads 23a and 23b.
• FIG. 3 depicts an array 25 of eight sensors like the sensor 21 of FIG. 2. Each sensor in the array has a unique formulation, such that it responds in a unique manner to any analyte brought into contact with the array. Representative response signals produced by the eight sensors in the array for one particular analyte are included in FIG. 3. These response signals are appropriately processed, as is described below, to identify the analyte to which the array is exposed. Thus, as shown in FIG.
• the eight sensors provide response signals that form a unique pattern, or "signature," for each of a variety of known analytes.
• the particular response signals that are produce for an unknown analyte are correlated with a library of known signatures, to determine the closest fit and, thereby, to identify the unknown analyte.
• Suitable circuitry for measuring the resistances of the sensor array 25 is disclosed in WO 99/47905, published September 23, 1999 and incorporated by reference for all purposes.
• conductive materials and nonconductive organic polymer materials can be used.
• Table 1 provides exemplary conductive materials for use in resistor fabrication; mixtures, such as of those listed, may also be used.
• Table 2 provides exemplary nonconductive organic polymer materials; blends and copolymers, such as of the polymers listed here, may also be used. Combinations, concentrations, blend stoichiometries, percolation thresholds, etc. are readily determined empirically by fabricating and screening prototype resistors (chemiresistors) as described below. Table 1.
• the application -specific hardware component includes such elements as sample delivery, sample heating (if necessary to achieve a certain vapor pressure), etc.
• Examples of the application-specific fluid delivery hardware includes: (1) a mask for breathalyzer type applications, (2) a wand for probe-type applications, and (3) a sample container in which sample processing (heating, cooling, etc.) could occur.
• the second sensor-based odor detection system i.e., the hand-held system, (FIG. 14B) incorporates a miniaturized sensor head placed on a silicon semiconductor chip.
• the sensor density on the chip must be increased for hand-held type applications from that of box-type applications. This can be achieved using PCB technology.
• More advanced handheld systems possess polymers with the proper sensing and electronic properties that have been placed on silicon chips. Inkjet technology is an example of technology that can be appropriated for this purpose.
• the selection of polymers for the array is application specific.
• the electronics of the hand-held system are essentially the electronics used in the tabletop system but with integrated signal processing.
• the miniaturization of the circuitry is accomplished using ASIC (Application Specific Integration Circuit) or other equivalent technology.
• ASIC Application Specific Integration Circuit
• the ASIC component requires more sophisticated design and engineering than the box-type sensor and is achieved by using known micro-process control technologies.
• the sensor array and the electronics are integrated so that as much signal processing as possible based upon the original sensed smell can be accomplished at the level of the sensor array itself. Signal processing carried out some distance from the sensor head results in lost signal strength and requires higher-powered electronics. The electronics required to compensate for this loss will lead to a higher-power solution than would be desirable for some applications and would likely force up unit manufacturing costs.
• the third sensor-based odor detection system could be integrated universally into almost any system where active, accurate or “smart” chemical sensing would offer product or service advantages or other economic benefit.
• This system contains a sensor array, an electrical measuring apparatus operatively associated with the sensor, and an information storage and processing device, all of which are incorporated on a single substrate such as a silicon chip.
• the chip-based system includes two chips, with its electronic functions divided between the two chips.
• One chip contains the sensor head, an application-specific, micro-machined mechanism to bring the smell to the chip in the required environment, and all signal processing electronics up until the point where the neural network takes over.
• the second chip contains a microprocessor or a neural network realized in silicon.
• the neural network can be etched into the silicon, which eliminates the requirement for a microprocessor to run the neural net software.
• a neural net on the chip and no microprocessor only micro-watt power will be required and the chip-based sensor system will be able to operate for very long periods on the equivalent of a watch battery.
• milli-watt power will be required and the chip-based sensor system will be able to run for shorter periods on the equivalent of four D-cells.
• Inkjet technology is preferred for placing a large number of polymer spots on a small area to form the sensor array.
• the spot density can be from around 10,000 spots in a one square centimeter area to less than one hundred, depending on the application and level of sensing required for the specific application.
• Another technique for forming the sensor array involves using a press to force-cut and simultaneously embed a sheet containing the different polymers into the sensor bed template.
• sensor-based odor detection systems have specific application in a variety of different technological fields, including the automotive, consumer products, consumer health care, environmental monitoring and remediation, food and beverage, and petrochemical, industries.
• sensor-based odor detection systems have applications in industrial manufacturing, law enforcement, and hazardous materials identification, as well as diagnostic applications in the medical field.
• the sensor technology is applicable to those molecules or odorants that have a detectable vapor pressure.
• the detection limit is on the order of parts per billion.
• analytes and fluids may be analyzed by the disclosed sensors, arrays and noses so long as the subject analyte is capable generating a differential response across a plurality of sensors of the array.
• Analyte applications include broad ranges of chemical classes such as organics such as alkanes, alkenes, alkynes, dienes, alicyclic hydrocarbons, arenes, alcohols, ethers, ketones, aldehydes, carbonyls, carbanions, polynuclear aromatics and derivatives of such organics, e.g., halide derivatives, etc.; biomolecules such as sugars, isoprenes and isoprenoids, fatty acids and derivatives, microorganisms, etc.
• commercial applications of the sensors, arrays and noses include environmental toxicology and remediation, biomedicine, materials quality control, food and agricultural products monitoring, etc.
• the sensors are generally applicable in two areas: (1) diagnostics and control applications; and (2) identification, categorization, and differentiation applications.
• the diagnostics and control applications e.g., cars, power plants, factories, pipelines, people, involve monitoring with feedback, the ebb and flow of chemicals in complex systems. These systems are made up of multiple sub-systems each containing different concentrations of different chemicals, where the separation of the sub-systems is critical for the function of the overall system.
• the chemical composition of the various monitoring environment may be changing constantly in an unknown and unknowable manner.
• the identification, categorization, and differentiation applications either are based upon specific molecular determinants that may or may not be known or are based upon complex unknown chemical mixtures, which may be changing over time.
• the first is a single-analyte detection system, which incorporates a sensor that detects the presence or absence of a single analyte, e.g., ethylene glycol (antifreeze) in engine radiators.
• the second is a multiple analyte detection system, which can differentiate among and identify various chemicals in a sample, e.g., differentiating an identification of individual hydrocarbons in a petroleum product.
• the third is a smart detection system, which can be programmed with enough information to be able to learn how to identify the key chemical features of its environment.
• An example is a food- cooking monitor that can identify the various smells and vapors from the cooking of an individual food and automatically stop cooking when the cooking is complete.
• the term smart denotes the integration, in part or in full, of the main processing unit which adds intelligence.
• the sensor itself has a data processing function and automatically calibrates and compensates for abnormalities.
• the sensor itself incorporates an algorithm, which is programmable and has a memory function. The sensor is coupled to other sensors in the array and adapts to changes in the environment and has discrimination functions.
• the smart sensors of the present invention perform logical functions and have microprocessors (e.g., Motorola 80HC11) "on board” or “on chip”.
• microprocessors e.g., Motorola 80HC11
• the integration of the microprocessor with the sensor is accomplished using ASIC technology.
• the smart sensors of the present invention possess the ability to communicate with other devices. This feature is advantageous because it allows the sensor to warn the user or adapt to changes in the environment using expert system methods, fuzzy logic or artificial neural networks.
• the smart sensors of the present invention have enhanced signal-to-noise ratios compared to sensors without integrated processing units.
• the "on board” or “on chip” processing capabilities reduces or eliminates the high input capacitance of transmission cables and other instrumentation.
• sensor-type applications that are not necessarily chip-based can be foreseen. These sensor-type applications do not require complicated electronics or signal processing to achieve the desired result, but merely indicate, in the same way as does a glucose test strip, that a certain level of a specific analyte is or is not present.
• the sensor-type applications can be further categorized by the type of fluid that is to be analyzed. Since the sensors are limited to the detection of vapors, the sensor- based odor detection devices must have specific hardware for delivering the sample to be analyzed.
• the sample delivery hardware is different for the vapor analysis of a gas, liquid, or solid sample. Specific examples of preferred embodiments for the sample delivery hardware, sensor head, and electronics for specific applications are described below. It is understood that the descriptions as provided below are given as examples of sensor-based odor detection devices and do not limit the invention to the devices represented below.
• a shield that keeps out the liquid being analyzed but admits its vapor must separate the liquid sample from the sensor.
• Examples of the type of shields that may be employed in the sensor hardware include gas-permeable metal-based screens, gas-permeable polymer-based membranes, or other devices and products that allow for the permeation of gases while excluding liquids.
• liquid-based samples may need to be heated to achieve a vapor pressure at which specific analytes may be detected.
• a sample chamber for containing a liquid sample and if necessary, heating the liquid sample to a suitable vapor pressure to analyze the fluid may also be employed in the fluid delivery apparatus.
• the integrated system contains a fluid delivery device that is associated with the substrate containing the sensor and possesses a miniature screening apparatus and optional sample vaporization hardware associated with the substrate.
• the sensing of gases is somewhat more straightforward in that the fluid being detected is already in the vapor form.
• the analysis of analyte already in the vapor phase requires capture and delivery of the gaseous fluid to the sensor array.
• capture and delivery devices include masks, probes, wands, tubes, and other devices that are capable of capturing and delivering gaseous fluids.
• part of the gaseous fluid delivery device may include hardware that condenses gaseous fluids and then revaporizes the fluid to achieve appropriate vapor concentration.
• One area of application for sensor-based odor detection devices is in the monitoring of engine fluids.
• Applications for chemical sensors exist wherever there is a liquid or a vapor that can leak or that can change in condition or quality over time. This includes any liquid and its vapor. These include, but are not limited to, detection of analytes in radiator fluid, engine oil, transmission fluid, gasoline, diesel fuel, etc.
• the sensors are used mainly in a diagnostic capacity, to improve engine performance and lower maintenance costs.
• the engine fluids would be separated from the sensor by a gas permeable shield.
• a small monitor could be installed in many regions adjacent to an engine separated from the fluid being measured by a shield that keeps out the fluid being analyzed but admits its vapor.
• a specific example of a sensor-based fluid detection device for use in an engine application includes an oil change monitor (see FIG. 15).
• the number one consumer request in the automotive maintenance industry is knowledge of when to change the oil. Differentiating between good oil, which is basic, and bad oil, which is acidic, is an easy-to- detect chemical change for the sensor-based fluid detection device.
• Such a sensor could be put in crankcase or actually in the oil filter, in which case it could be a disposable product.
• Monitoring the oil quality would enable oil changes to be performed no sooner than when they are actually required.
• the detection of oil quality would result from a direct readout of the chemistry of the oil, rather than as is the case with some current detectors, which are based upon an algorithm that uses time, ignition firing, rpm, temperature, etc., to derive a result.
• a sensor could be placed in a radiator cap to determine if sufficient antifreeze (ethylene glycol) is present.
• antifreeze ethylene glycol
• the radiator cap could simply incorporate a chip tuned for ethylene glycol concentration. This would counteract user error in providing a warning when insufficient antifreeze is present. This is an especially useful application in extreme climates, where insufficient antifreeze can cause significant engine damage.
• Control application sensors collect information from a certain environment within an engine, and then feed this information to on-board computers, which in turn use the information to manage and optimize the engine's operation.
• the information could be used to diagnose engine problems, fluid quality problems, etc.
• Diesel engines can burn many fuels, but their mechanical durability is based upon the presence or absence of a few key elements in the fuel. These elements include certain sulfur compounds, asphaltenes, and other elements, which effectively polymerize and function as engine lubricants. Sensing them is critical to maintaining engine longevity.
• the sensors can distinguish among various different hydrocarbon species, e.g., asphaltenes vs. diasphaletenes vs. parafins vs. olefins, etc., and engine operation can be adjusted in accordance with the sensed fuel components.
• the sensor-based fluid detection device is used for monitoring and detecting emissions from combustion processes.
• Polymer-based sensors can be placed in either the engine intake (FIG. 17) or the exhaust (FIG. 18) for use in clean-burn emissions control.
• the sensor located in the engine intake would not measure emissions directly. Rather, the measurements taken at the intake would be put through a neural network using the automobile's on-board computer and would impute emissions quality from the sensor information and information from other sensors present in the automobile.
• Sensors could also be placed in the exhaust, but high temperature exhaust systems would require insulation of the sensor from the harsh temperature environment. Examples of such combustion processes include automotive gasoline and diesel engines as well as industrial combustion processes such as power plant emissions.
• the sensors also could detect catalyst function and readily determine if conversion of combustion products such as volatile organic compounds (VOC's) is complete.
• VOC's volatile organic compounds
• a small integrated sensor that could detect emissions products such as VOC's, NO x , SO x , CO and water, for example, could alert engine operators and industrial combustion operators (e.g., power plant operators), whether combustion is complete and if the emission reducing catalytic converters are functioning properly.
• Metal oxide sensors are used currently for some applications, e.g., monitoring exhaust gases. Their disadvantage, when as application-specific sensors, is cost and the requirement that they be heated. This can lead them to act as an ignition source, which is dangerous in areas such as this with combustible gases.
• the sensor- based fluid detection system is used for monitoring and detecting emissions from food cooking and heating processes.
• the sensor is employed in microwave cooking without the need to set temperature or time.
• One button operation of microwave cooking would be possible, i.e., "Cook” with a sensor for humidity, which is essentially, water vapor.
• the neural network predicts the temperature rise profile, and in a control loop adjusts the amount of heating (microwave energy) required.
• the sensor-based fluid detection array would be combined with a neural network programmed to optimally cook a whole spectrum of food types, along with profiles of their evolving smells as they cook. For example, green beans would be placed into the microwave oven and the oven recognizes the first vapors of green beans beginning to cook and follows the green bean optimal microwave energy profile. Ongoing monitoring would enable real-time adjustment, i.e., as the green beans approach being fully cooked, they could be tested by the smell sensor and energy reduced or increased and the cooking time modified. In this way, food thickness, wetness and other qualities could be automatically adjusted for.
• a sensor-based odor detection device comprised of a sensor, a fluid delivery device, an electronic measuring device, and an information storage and processing device can detect the presence of human breath vapors.
• Neural network software attached to the sensor array can compare the human breath vapors with a library of bad breath smells and provide a response to indicate the presence of unpleasant odors.
• Another preferred embodiment is a sensor-based fluid detection device for soil analysis (see FIG. 21).
• Organic soil contaminants are currently analyzed using lab-based gas chromatography.
• a portable sensor-based fluid detection device would allow for on-site analysis of soil contamination.
• a sensor-based fluid detection device can detect contaminants found at contaminated sites either by a box-type sensor, which could detect the presence of any volatile soil contaminants, or by a higher level sensor that would be able to separately detect individual analytes in a soil sample. This is particularly useful in soil remediation applications, where rapid, automated, parallel processing of multiple analytes in the field is desirable.
• Another preferred embodiment is a sensor-based fluid detection device for environmental monitoring (see FIG. 22).
• Environmental monitoring and air quality control of atmospheric gases such as water vapor (humidity), CO, oxygen, ozone, etc., as well as volatile organic chemicals (solvents) and noxious or unpleasant gases, could be performed by a sensor-based fluid detection device.
• the sensors have a variety of useful settings including homes, office buildings, industrial manufacturing facilities, laboratories, etc., and could be installed in thermostats or as a separate environmental monitoring unit.
• the senor could be part of an active feedback loop, especially for homes or buildings with modern HNAC systems.
• the air quality sensor would function in a manner similar to a thermostat. Recirculation, oxygen and carbon dioxide levels could be continuously monitored and adjusted, just as temperature is currently monitored and adjusted using a thermostat.
• Another example of an environmental monitoring application is in the passenger cabins of automobiles and airplanes, or other small self-contained environments.
• a sensor that detects atmospheric vapors such as humidity, carbon monoxide, and oxygen, in combination with a sensor that detects noxious or unpleasant vapors and a recirculation fresh air control device, depending on the indoor/outdoor air quality is an example of an embodiment useful for automobiles or other enclosed spaces.
• a sensor device in an automobile upon passing an odiferous garbage truck, would detect the odor and immediately switch the environmental control from "Fresh Air” to "Recirculate.” Conversely, the sensing device, upon detecting excess carbon monoxide in the automobile compartment, would automatically switch to "Fresh Air.”
• the sensor devices also are applicable to petroleum refining plants, laboratories, and industrial manufacturing plants where volatile chemicals are used and monitored (see FIG. 24).
• a sensor-based odor detection device particularly a portable device, could be used for inspecting and monitoring for fluid leakage and spills.
• a related application for the sensors is detecting leaks in underground storage tanks, pipelines and other relatively inaccessible processing and storage facilities for hazardous chemicals such as petrochemicals.
• Chemical plants are yet another example of complex systems where on-line chemical monitoring is useful, either to actuate alarms or to be made part of active process control feedback loops.
• Monitors for industrial coatings, paint and curing processes can employ the same basic sensor technology. Currently, these processes are monitored based on a recipe (time and temperature). A sensor-based fluid detection device could alert plant operators when the processes were complete, e.g., actuate a notification device when the paint is dry, the plastic cured, etc. Installed models would be useful for drying rooms in industrial plants and on assembly lines.
• Sensor-based detectors that determine the presence and/or identity of hazardous materials are useful for fire safety, chemical weapons identification, and for hazardous material teams.
• the sensors can be tuned to detect noxious poisonous vapors from indoor fires and to warn firefighters or building occupants.
• Hazmat detectors would find ready use in laboratories for spill detection and in many industrial facilities where chemicals are used.
• Disposable cartridges may be used to assure the integrity of the unit following each deployment. Bomb squads could use the detectors to identify explosives (e.g., TNT) from a remote sensing position, e.g., employing robotics.
• explosives e.g., TNT
• chemical sensors could be incorporated into chemical warfare protective suit, or hazmat suits, on the inside and/or on the outside, to determine chemical presence, suit leakage, and contamination.
• These sensor devices can contain neural network software, and the sensor and the electronics can be configured to the needs of each hazmat detection device.
• the sensors can detect spoiled food, or food that does not conform to a specified smell profile. Examples include: E. coli in meat; salmonella in chicken; botulinum in canned goods; spoilage of dairy products; fish freshness; etc.
• the sensor device may be a disposable, sensor-type application or an integrated monitoring device. An example of this embodiment is in the screening of recyclable bottles for contaminants that have residual odors.
• the sensor devices could also be installed in assembly lines with multiple sensors for mass production applications. Another embodiment is in batch-to-batch consistency of food products. For example, products that are currently tested by either food or beverage tasters and smellers could be monitored with sensor devices to determine whether the particular batch conforms with an ideal response profile. Additionally, any manufacturing processes that can be controlled by odor detection has an applicable sensor device use. Examples include perfume manufacturing, gases for semiconductor fabs, network pipeline feedstocks, and bio-feeds.
• Diagnostic breathalyzer devices for medical and law enforcement uses is another embodiment of the sensor-based fluid detection devices (see FIG. 31).
• a breathalyzer that differentiates between ethanol and toluene is needed in law enforcement. Toluene poisoning leads to symptoms of ethanol intoxication, but is not illegal. This can cast doubt on the prosecution's evidence, sometimes leading to acquittal.
• a sensor-based breathalyzer could establish ethanol intoxication beyond a reasonable doubt and assist in prosecuting drunk drivers.
• the sensor device could have minimum electronics and no neural network, e.g., an ethanol sensor array that simply provides a positive response to ethanol.
• Medical applications for sensor-based fluid detection involves incorporation into devices for diagnosis and monitoring of patient conditions and diseases (see FIGS. 32- 33).
• the devices would be suitable for doctor's office use, bedside applications, and for acute response medicine, including installation in ambulances.
• respiratory bacterial infections could be quickly diagnosed from breathalyzer analysis and distinguished from other medical conditions.
• Other conditions for diagnosis and monitoring using a breathalizer- type apparatus equipped with smell-detecting cartridges or chips keyed for specific applications include peptic ulcer disease, uremia, ketone levels in diabetes mellitus, exposure to toxic substances, liver disease, and cancers.
• Bacterial skin conditions are diagnosable using sensor devices and can distinguish bacterial from non-bacterial conditions. Monitoring pre-epileptic and pre -manic states through sweat monitoring, e.g., bracelets or necklaces worn by at-risk individuals is an example of another use.
• the sensor device include portable sensing devices with a fluid delivery appliance, or an integrated disposable sensor device that could be incorporated into bandages.
• Chip-based sensors for use in medical diagnostics are an example of another embodiment (See FIG. 34).
• the sensor device may be integrated into a catheter for examination purposes. This use employs sensor-based probes that may be swallowed, surgically inserted into the body, or inserted into the body through a natural orifice.
• the sensor device may be coupled with surgical tools, endoscopes, or other surgical devices for diagnosis and consequential medical treatment.
• Implantable monitors constitute another chip-based embodiment. These implantable monitors can monitor blood gases and alert patients or health care workers when out of specification sensor detection occurs.
• the sensor-based fluid detection devices also can be used to detect the presence of ethylene oxide gas. Residual ethylene oxide is a problem in sterilization procedures.
• a sensor-based fluid detection device with a wand could be used to detect the presence of ethylene oxide in sterilized instruments.
• the sensor device may be a tabletop device or a portable device.
• disposable sensor cartridges may be used to detect residual ethylene oxide gas.
• Plasticized poly(pyrrole) sensors were made by mixing two solutions, one of which contained 0.29 mmoles pyrrole in 5.0 ml tetrahydrofuran, with the other containing 0.25 mmoles phosphomolybdic acid and 30 mg of plasticizer in 5.0 ml of tetrahydrofuran. The mixture of these two solutions resulted in a w:w ratio of pyrrole to plasticizer of 2:3.
• An inexpensive, quick method for crating the chemiresistor array elements was accomplished by effecting a cross sectional cut through commercial 22 nF ceramic capacitors (Kemet Electronics Corporation).
• a data set obtained from a single exposure of the array to an odorant produced a set of descriptors (i.e., resistances), d;.
• the data obtained from multiple exposures thus produced a data matrix D where each row, designated by j, consisted of n descriptors describing a single member of the data set (i.e., a single exposure to an odor). Since the baseline resistance and the relative changes in resistance varied among sensors, the data matrix was autoscaled before further processing (see, Hecht (1990) Mathematics in Chemistry: An Introduction to Modern Methods (Prentice Hall, Englewood Cliffs, NJ)). In this preprocessing technique, all the data associated with a single descriptor (i.e., a column in the data matrix) were centered around zero with unit standard deviation
• This operation produced the correlation matrix, R whose diagonal elements were unity and whose off-diagonal elements were the correlation coefficients of the data.
• the total variance in the data was thus given by the sum of the diagonal elements in R.
• the n eigenvalues, and the corresponding n eigenvectors, were then determined for R.
• Each eigenvector contained a set of n coefficients which were used to transform the data by linear combination into one of its n principle components.
• the corresponding eigenvalue yielded the fraction of the total variance that was contained in that principle component.
• This operation produced a principle component matrix, P, which had the same dimensions as the original data matrix. Under these conditions, each row of the matrix P was still associated with a particular odor and each column was associated with a particular principle component.
• FIG. 2 shows the cyclic voltammetric behavior of a chemically polymerized poly(pyrrole) film following ten cycles from -1.00 V to +0.70 N vs. SCE.
• the cathodic wave at -0.40 V corresponded to the reduction of poly(pyrrole) to its neutral, nonconducting state
• the anodic wave at -0.20 N corresponded to the reoxidation of poly(pyrrole) to its conducting state (see, Kanazawa et al (1981) Synth. Met. 4:119-130).
• the lack of additional faradaic current which would result from the oxidation and reduction of phosphomolybdic acid in the film, suggests that the
• Keggin structure of phosphomolybdic acid was not present in the film anions (see, Bidan et al. (1988) J Electroanal Chem. 251:297-306) and implies that MoO 4 2" , or other anions, served as the poly(pyrrole) counterions in the polymerized films.
• FIG. 3 A shows the optical spectrum of a processed polypyrrole film that had been spin-coated on glass and then rinsed with methanol.
• the single absorption maximum was characteristic of a highly oxidized poly(pyrrole) (see, Kaufman et al. (1984) Phys. Rev. Lett. 53:1005-1008), and the absorption band at 4.0 eV was characteristic of an interband transition between the conduction and valence bands.
• the lack of other bands in this energy range was evidence for the presence of bipolaron states (see FIG. 3 A), as have been observed in highly oxidized poly yrrole) (see, Kaufman et al. ( 1984) Phys. Rev. Lett. 53 : 1005- 1008).
• Sensor arrays consisted of as many as 14 different elements, with each element synthesized to produce a distinct chemical composition, and thus a distinct sensor response, for its polymer film.
• the resistance, R, of each film-coated individual sensor was automatically recorded before, during, and after exposure to various odorants.
• a typical trial consisted of a 60 sec rest period in which the sensors were exposed to flowing air (3.0 liter-min "1 ), a 60 sec exposure to a mixture of air (3.0 liter-min "1 ) and air that had been saturated with solvent (0.5 - 3.5 liter-min "1 ), and then a 240 sec exposure to air (3.0 liter-min "1 ).
• FIGS. 4B-4D depict representative examples of sensor amplitude responses of a sensor array (see, Table 3).
• An exposure consisted of: (i) a 60 sec rest period in which the sensors were exposed to flowing air (3.0 liter-min "1 ); (ii) a 60 sec exposure to a mixture of air (3.0 liter-min “1 ) and air that had been saturated with solvent (0.5 liter-min "1 ); and (iii) a 240 sec exposure to air (3.0 liter-min "1 ). It is readily apparent that these odorants each produced a distinctive response on the sensor array.
• Table 3 The units along the axes indicate the amplitude of the principle component that was used to describe the particular data set for an odor.
• the black regions indicate clusters corresponding to a single solvent which could be distinguished from all others; gray regions highlight data of solvents whose signals overlapped with others around it. Exposure conditions were identical to those in FIG. 4.
• FIG. 6 shows the principle component analysis for all 14 sensors described in Table 3 and FIGS. 4 and 5.
• FIG. 6A or 6B When the solvents were projected into a three dimensional odor space (FIG. 6A or 6B), all eight solvents were easily distinguished with the specific array discussed herein. Detection of an individual test odor, based only on the criterion of observing -1% ⁇ R max /R, values for all elements in the array, was readily accomplished at the parts per thousand level with no control over the temperature or humidity of the flowing air. Further increases in sensitivity are likely after a thorough utilization of the temporal components of the ⁇ R max /R, data as well as a more complete characterization of the noise in the array.
• This type of polymer-based array is chemically flexible, is simple to fabricate, modify, and analyze, and utilizes a low power dc resistance readout signal transduction path to convert chemical data into electrical signals. It provides a new approach to broadly-responsive odor sensors for fundamental and applied investigations of chemical mimics for the mammalian sense of smell. Such systems are useful for evaluating the generality of neural network algorithms developed to understand how the mammalian olfactory system identifies the directionality, concentration, and identity of various odors.
• a sensor exposure consisted of (1) a 60 second exposure to flowing air (6 liter min-1), (2) a 60 second exposure to a mixture of air (6 liter min-1) and air that had been saturated with the analyte (0.5 liter min-1), (3) a five minute recovery period during which the sensor array was exposed to flowing air (6 liter min-1).
• the resistance of the elements were monitored during exposure, and depending on the thickness and chemical make-up of the film, resistance changes as large as 250% could be observed in response to an analyte.
• a 10 element sensor array consisting carbon-black composites formed with a series of non- conductive polymers (see Table 4) was exposed to acetone, benzene, chloroform, ethanol, hexane, methanol, and toluene over a two day period. A total of 58 exposures to these analytes were performed in this time period. In all cases, resistance changes in response to the analytes were positive, and with the exception of acetone, reversible (see FIG. 8). The maximum positive deviations were then subjected to principal component analysis in a manner analogous to that described for the poly(pyrrole) based sensor.
• FIG. 9 shows the results of the principal component analysis for the entire 10-element array.

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