Brett J. Doleman

Comparison of odor detection thresholds and odor discriminablities of a conducting polymer composite electronic nose versus mammalian olfaction

Abstract Response data from an array of conducting polymer composite vapor detectors that form an electronic nose were collected for the purpose of comparing selected, quantitatively measurable, phenomena in odor detection and classification to the olfactory characteristics of monkeys and humans. Odor detection thresholds and discriminability between structurally similar pairs of odorants were the two primary quantities evaluated for this comparison. Comparisons were only made for volatile organic vapors as opposed to aroma active odorant vapors. Electronic nose detection thresholds for a homologous series of n-alkane and 1-alcohol odorants were determined and the results were compared to literature values for the mean olfactory detection thresholds observed in psychophysical experiments on humans exposed to these same vapors. The trends in odor detection thresholds of the electronic nose towards the tested analytes were very similar to those exhibited by humans. The discrimination performance of the electronic nose for distinguishing between pairs of odorants within incrementally varying series of esters, carboxylic acids and alcohols were also compared to the published data of Laska and co-workers on the psychophysical performance of humans and monkeys for these same odorant pairs. Similar trends were generally observed between the humans, monkeys, and the electronic nose in that discrimination performance increased as the compounds of an odorant pair became more structurally dissimilar. With use of the Fisher linear discriminant algorithm for classification of these test pairs of odorants, the electronic nose exhibited significantly better discriminability than humans or monkeys for the odorant pairs evaluated in this work under the test conditions for which the discriminability was evaluated.

Assessing the ability to predict human percepts of odor quality from the detector responses of a conducting polymer composite-based electronic nose

Abstract The responses of a conducting polymer composite “electronic nose” detector array were used to predict human perceptual descriptors of odor quality for a selected test set of analytes. The single-component odorants investigated in this work included molecules that are chemically quite distinct from each other, as well as molecules that are chemically similar to each other but which are perceived as having distinct odor qualities by humans. Each analyte produced a different, characteristic response pattern on the electronic nose array, with the signal strength on each detector reflecting the relative binding of the odorant into the various conducting polymer composites of the detector array. A “human perceptual space” was defined by reference to English language descriptors that are frequently used to describe odors. Data analysis techniques, including standard regression, nearest-neighbor prediction, principal components regression, partial least squares regression, and feature subset selection, were then used to determine mappings from electronic nose measurements to this human perceptual space. The effectiveness of the derived mappings was evaluated by comparison with average human perceptual data published by Dravnieks. For specific descriptors, some models provided cross-validated predictions that correlated well with the human data (above the 0.60 level), but none of the models could accurately predict the human values for more than a few descriptors.

Array-Based Vapor Sensing Using Chemically Sensitive, Carbon Black−Polymer Resistors

We describe herein the construction of a simple, low-power, broadly responsive vapor sensor. Carbon black-organic polymer composites have been shown to swell reversibly upon exposure to vapors. Thin films of carbon black-organic polymer composites have been deposited across two metallic leads, with swelling-induced resistance changes of the films signaling the presence of vapors. To identify and classify vapors, arrays of such vapor-sensing elements have been constructed, with each element containing the same carbon black conducting phase but a different organic polymer as the insulating phase. The differing gas-solid partition coefficients for the various polymers of the sensor array produce a pattern of resistance changes that can be sued to classify vapors and vapor mixtures. This type of sensor array has been shown to resolve common organic solvents, including molecules of different classes as well as those within a particular class.

Differential Detection of Enantiomeric Gaseous Analytes Using Carbon Black-Chiral Polymer Composite, Chemically Sensitive Resistors

Carbon black-chiral polymer composites were used to provide diagnostic differential resistance responses in the presence of enantiomers of chiral gaseous analytes. Vapors of (+)-2-butanol and (-)-2-butanol, (+)-α-pinene and (-)-α-pinene, (+)-epichlorohydrin and (-)-epichlorohydrin, and methyl (+)-2-chloropropionate and methyl (-)-2-chloropropionate were generated and passed over a chemically sensitive carbon black-poly((R)-3-hydroxybutyrate-co-(R)-3-hydroxyvalerate) (77% butyrate) composite resistor. Each enantiomer of a pair produced a distinct relative differential resistance change on the chiral detector, whereas both enantiomers of a set produced identical signals on achiral carbon black-poly(ethylene-co-vinyl acetate) (82% ethylene) detectors.

Array-based vapor sensing using chemically sensitive, polymer composite resistors

We describe herein the construction of simple, low-power, broadly responsive vapor sensors. Insulating polymer-conductor composites have been shown to swell reversibly upon exposure to vapors. Thin films of polymer composites have been deposited across two metallic leads, with swelling-induced resistance changes of the films signaling the presence of vapors. To identify and classify vapors, arrays of such vapor-sensing elements have been constructed, with each element containing either carbon black or poly(pyrrole) as the conducting phase mixed with one of several different organic polymers as the insulating phase. A convenient chemical polymerization of poly(pyrrole) which allows a high degree of processibility is also described. The differing gas-solid partition coefficients for the various polymers of the sensor array produce a pattern of resistance changes that can be used to classify vapors and vapor mixtures. This type of sensor array has been shown to resolve common organic solvents, including molecules of different classes (such as aromatics from alcohols) as well as those within a particular class (such as benzene from toluene and methanol from ethanol). The response of an individual composite to varying concentrations of solvent is shown to be consistent with the predictions of percolation theory. Accordingly, significant increases in the signals of array elements have been observed for carbon black-polymer composites that were operated near their percolation thresholds.

Mimicking the sense of olfaction: A conducting-polymer-based electronic nose

— We describe herein the construction of a simple, low-power, broadly responsive vapor sensor. Carbon-black-organic-polymer composites have been shown to swell reversibly upon exposure to vapors. Thin films of carbon-black-organic-polymer composites have been deposited across two metallic leads, with swelling-induced resistance changes of the films signaling the presence of vapors. To identify and classify vapors, arrays of such vapor-sensing elements have been constructed, with each element containing a different organic polymer as the insulating phase. The differing gas-solid partition coefficients for the various polymers of the sensor array produce a pattern of resistance changes that can be used to classify vapors and vapor mixtures. This type of sensor array has been shown to resolve all organic vapors that have been analyzed, and can even resolve H2O from D2O.

Progress in the development of an electronic nose using arrays of chemically sensitive carbon black-polymer resistors

Response data were collected for a carbon black-polymer composite electronic nose array during exposure to homologous series of alkanes and alcohols. At a fixed partial pressure of odorant in the vapor phase, the mean response intensity of the electronic nose signals varied significantly for members of each series of odorants. However, the mean response intensity of the electronic nose detectors, and the response intensity of the most strongly-driven set of electronic nose detectors, was essentially constant for members of a chemically homologous odorant series when the concentration of each odorant in the gas phase was maintained at a constant fraction of the odorants vapor pressure. Because the thermodynamic activity of an odorant at equilibrium in a sorbent phase is equal to the partial pressure of the odorant in the gas phase divided by the vapor pressure of the odorant, and because the activity coefficients are similar within these homologous series of odorants for sorption of the vapors into specific polymer films, the data imply that the trends in detector response can be understood based on the thermodynamic tendency to establish a relatively constant concentration of sorbed odorant into each of the polymeric films of the electronic nose at a constant fraction of the odorants vapor pressure. This phenomenon provides a natural mechanism for enhanced sensitivity to low vapor pressure compounds, like TNT, in the presence of high vapor pressure analytes, such as diesel fuel. In a related study to evaluate the target recognition properties of the electronic nose, a statistical metric based on the magnitudes and standard deviations along Euclidean projections of clustered array response data, was utilized to facilitate an evaluation of the performance of detector arrays in various vapor classification tasks. This approach allowed quantification of the ability of a fourteen-element array of carbon black-insulating polymer composite chemiresistors to distinguish between members of a set of nineteen solvent vapors, some of which vary widely in chemical properties (e.g. methanol and benzene) and others of which are very similar (e.g. n-pentane and n-heptane). The data also facilitated evaluation of questions such as array performance as a function of the number of detectors in the system.

Sensing and Discrimination of Vapors by an Array of Conducting Carbon Black‐Polymer Composites

We describe herein the construction of a simple, low-power, broadly responsive vapor sensor. Carbon black-organic polymer composites have been shown to swell reversibly upon exposure to vapors. Thin films of carbon black-organic polymer composites have been deposited across two metallic leads, with swelling-induced resistance changes of the films signaling the presence of vapors. To identify and classify vapors, arrays of such vapor-sensing elements have been constructed, with each element containing a different organic polymer as the insulating phase. The differing gas-solid partition coefficients for the various polymers of the sensor array produce a pattern of resistance changes that can be used to classify vapors and vapor mixtures. This type of sensor array has been shown to resolve all organic vapors that have been analyzed, and can even resolve H2O from D2O.