Kenneth Manatt

Molecular modeling of polymer composite–analyte interactions in electronic nose sensors

We report a molecular modeling study to investigate the polymer-carbon black (CB) composite-analyte interactions in resistive sensors. These sensors comprise the JPL electronic nose (ENose) sensing array developed for monitoring breathing air in human habitats. The polymer in the composite is modeled based on its stereoisomerism and sequence isomerism, while the CB is modeled as uncharged naphthalene rings with no hydrogens. The Dreiding 2.21 force field is used for the polymer, solvent molecules and graphite parameters are assigned to the carbon black atoms. A combination of molecular mechanics (MM) and molecular dynamics (NPT-MD and NVT-MD) techniques are used to obtain the equilibrium composite structure by inserting naphthalene rings in the polymer matrix. Polymers considered for this work include poly(4-vinylphenol), polyethylene oxide, and ethyl cellulose. Analytes studied are representative of both inorganic and organic compounds. The results are analyzed for the composite microstructure by calculating the radial distribution profiles as well as for the sensor response by predicting the interaction energies of the analytes with the composites.

Operation of an Electronic Nose Aboard the Space Shuttle and Directions for Research for a Second Generation Device

A flight experiment to test the operation of an Electronic Nose developed and built at JPL and Caltech was done aboard STS-95 in October-November, 1998. This ENose uses conductometric sensors made of insulating polymer-carbon composite films; it has a volume of 1.7 liters, weighs 1.4 kg including the operating computer and operates on 1.5 W average power. In the flight experiment, the ENose was operated continuously for 6 days and recorded the sensors’ response to changes in air in the mid-deck of the orbiter. The ENose had been trained to identify and quantify ten common contaminants at the 24-hour Spacecraft Maximum Allowable Concentration (SMAC) level. Most SMACs are on the order of 10-100 ppm. The experiment was controlled by collecting air samples daily and analyzing them using standard analytical techniques after the flight. The device is microgravity insensitive.

Correlating Polymer-Carbon Composite Sensor Response with Molecular Descriptors

We report a quantitative structure-activity relationships QSAR study using genetic function approximations to describe the activities of a polymer-carbon composite chemical vapor sensor using a novel approach to selecting a molecular descriptor set. The measured sensor responses are conductivity changes in polymer-carbon composite films upon exposure to target vapors at partsper-million concentrations. The descriptor set combines the basic analyte descriptor set commonly used in QSAR studies with descriptors for sensing film-analyte interactions. The basic analyte descriptors are obtained using a combination of empirical and semiempirical quantitative structure-property relationships methods. The descriptors for the sensing film-analyte interactions are calculated using molecular modeling and simulation tools. A statistically validated QSAR model was developed for a training data set consisting of 17 analyte molecules. The applicability of this model was also tested by predicting sensor activities for three test analytes not considered in the training set.

Monitoring Space Shuttle Air for Selected Contaminants Using an Electronic Nose

A miniaturized electronic nose has been constructed at JPL in collaboration with Caltech. This array of conductometric sensors has been trained to detect and quantify the presence of vapors in the air; the compounds detected have been found as contaminants in shuttle air. This device has potential application as a miniature, distributed device for monitoring and controlling the constituents in air.

Expanding the capabilities of the JPL electronic nose for an International Space Station technology demonstration

An array-based sensing system based on polymer/carbon composite conductometric sensors is under development at JPL for use as an environmental monitor in the International Space Station. Sulfur dioxide has been added to the analyte set for this phase of development. Using molecular modeling techniques, the interaction energy between SO2 and polymer functional groups has been calculated, and polymers selected as potential SO2 sensors. Experiment has validated the model and two selected polymers have been shown to be promising materials for SO2 detection.

Toward A Second Generation Electronic Nose at JPL: Sensing Film Optimization Studies

Development of a second generation Electronic Nose at JPL is focusing on optimization of the sensing films to increase sensitivity and optimization of the array. Toward this goal, studies have focused on sources of noise in the films, alternatives to carbon black as conductive medium, measurement techniques, and development of an analytical approach to polymer selection to maximize the abilities of the array to distinguish among compounds. methods of data acquisition, and selection of polymers for films in the sensing array. Sensing film optimization studies to increase sensitivity have been focused primarily on decreasing noise in the response. Studies with this goal have included investigation of the sensor films and of measurement methods. Studies of the films include studies of the polymers used in the films and of the fabrication methods, including consideration of several materials as possible replacements for carbon black as the conductive medium in the film, including noble metals, metal oxides and carbon nanotubes. Studies of measurement techniques have investigated the use of AC methods to follow sensor response. The first JPL ENose used DC measurements to monitor resistance changes in the sensing films. AC measurements of thin films can be more sensitive to changes at the interface of the electrodes and the films, and so AC techniques were considered for data acquisition.

Development of the Third Generation JPL Electronic Nose for International Space Station Technology Demonstration

The capabilities of the JPL Electronic Nose have been expanded to include characteristics required for a Technology Demonstration schedule on the International Space Station (ISS) in 2008-2009 [1,2]. Concurrently, to accommodate specific needs on ISS, the processes, tools and analyses which influence all aspects of development of the device have also been expanded. The Third Generation ENose developed for this program uses two types of sensor substrates, newly developed inorganic and organic sensor materials, redesigned electronics, onboard near real-time data analysis and power and data interfaces specifically for ISS. This paper will discuss the Third Generation ENose with a focus on detection of mercury in the parts-per-billion range.

Expanding the Analyte Set of the JPL Electronic Nose to Include Inorganic Species

An array-based sensing system based on 32 polymer/carbon composite conductometric sensors is under development at JPL. Until the present phase of development, the analyte set has focused on organic compounds (common solvents) and a few selected inorganic compounds, notably ammonia and hydrazine. The present phase of JPL ENose development has added two inorganics to the analyte set: mercury and sulfur dioxide. Through models of sensor-analyte response developed under this program coupled with a literature survey, approaches to including these analytes in the ENose target set have been determined.

The JPL electronic nose: Monitoring air in the U.S. Lab on the International Space Station

An electronic nose with a sensor array of 32 conductometric sensors has been developed at the Jet Propulsion Laboratory (JPL) to monitor breathing air in spacecraft habitat. The Third Generation ENose is designed to operate in the environment of the U.S. Lab on the International Space Station (ISS). It detects a selected group of analytes at target concentrations in the ppm regime at an environmental temperature range of 18 – 30 °C, relative humidity from 20 – 75% and pressure from 530 to 760 torr. The monitoring targets are anomalous events such as leaks and spills of solvents, coolants or other fluids. The JPL ENose operated as a technology demonstration for seven months in the U.S. Laboratory Destiny during 2008–2009. Analysis of ENose monitoring data shows that there was regular, periodic rise and fall of humidity and occasional releases of Freon 218 (perfluoropropane), formaldehyde, methanol and ethanol. There were also several events of unknown origin, half of them from the same source. Each event lasted from 20 to 100 minutes, consistent with the air replacement time in the U.S. Lab.

Ground Validation of the Third Generation JPL Electronic Nose

The Third Generation ENose is an air quality monitor designed to operate in the environment of the US Lab on the International Space Station. It detects a selected group of analytes at target concentrations in the ppm regime at an environmental temperature range of 18 30 o C, relative humidity from 25 - 75% and pressure from 530 to 760 torr. The abilities of the device to detect ten analytes, to reject confounders as “unknown” and to deconvolute mixtures of two analytes under varying environmental conditions has been tested extensively in the laboratory. Results of ground testing showed an overall success rate for detection, identification and quantification of analytes of 87% under nominal temperature and humidity conditions and 83% over all conditions.