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Polymers for Chemical Sensors Using Hydrosilylation Chemistry

Description: Sorbent and functionalized polymers play a key role in a diverse set of fields, including chemical sensors, separation membranes, solid phase extraction techniques, and chromatography. Sorbent polymers are critical to a number of sensor array or "electronic nose" systems. The responses of the sensors in the array give rise to patterns that can be used to distinguish one compound from another, provided that a sufficiently diverse set of sensing materials is present in the array. Figure 1 illustrates the concept of several sensors, each with a different sensor coating, giving rise to variable responses to an analyte that appear as a pattern in bar graph format. Using hydrosilylation as the bond-forming reaction, we have developed a versatile and efficient approach to developing sorbent polymers with diverse interactive properties for sensor applications. Both the chemical and physical properties of these polymers are predictable and tunable by design.
Date: June 28, 2001
Creator: Grate, Jay W.; Kaganove, Steven N. & Nelson, David A.
Partner: UNT Libraries Government Documents Department

Biological detection and tagging using tailorable, reactive, highly fluorescent chemosensors.

Description: This program was focused on the development of a fluorogenic chemosensor family that could tuned for reaction with electrophilic (e.g. chemical species, toxins) and nucleophilic (e.g. proteins and other biological molecules) species. Our chemosensor approach utilized the fluorescent properties of well-known berberine-type alkaloids. In situ chemosensor reaction with a target species transformed two out-of-plane, weakly conjugated, short-wavelength chromophores into one rigid, planar, conjugated, chromophore with strong long wavelength fluorescence (530-560 nm,) and large Stokes shift (100-180 nm). The chemosensor was activated with an isourea group which allowed for reaction with carboxylic acid moieties found in amino acids.
Date: November 1, 2006
Creator: Shepodd, Timothy J.; Zifer, Thomas; McElhanon, James Ross & Rahn, Larry A.
Partner: UNT Libraries Government Documents Department

Micro flame-based detector suite for universal gas sensing.

Description: A microflame-based detector suit has been developed for sensing of a broad range of chemical analytes. This detector combines calorimetry, flame ionization detection (FID), nitrogen-phosphorous detection (NPD) and flame photometric detection (FPD) modes into one convenient platform based on a microcombustor. The microcombustor consists in a micromachined microhotplate with a catalyst or low-work function material added to its surface. For the NPD mode a low work function material selectively ionizes chemical analytes; for all other modes a supported catalyst such as platinum/alumina is used. The microcombustor design permits rapid, efficient heating of the deposited film at low power. To perform calorimetric detection of analytes, the change in power required to maintain the resistive microhotplate heater at a constant temperature is measured. For FID and NPD modes, electrodes are placed around the microcombustor flame zone and an electrometer circuit measures the production of ions. For FPD, the flame zone is optically interrogated to search for light emission indicative of deexcitation of flame-produced analyte compounds. The calorimetric and FID modes respond generally to all hydrocarbons, while sulfur compounds only alarm in the calorimetric mode, providing speciation. The NPD mode provides 10,000:1 selectivity of nitrogen and phosphorous compounds over hydrocarbons. The FPD can distinguish between sulfur and phosphorous compounds. Importantly all detection modes can be established on one convenient microcombustor platform, in fact the calorimetric, FID and FPD modes can be achieved simultaneously on only one microcombustor. Therefore, it is possible to make a very universal chemical detector array with as little as two microcombustor elements. A demonstration of the performance of the microcombustor in each of the detection modes is provided herein.
Date: November 1, 2005
Creator: Hamilton, Thomas Warren; Washburn, Cody M.; Moorman, Matthew Wallace; Manley, Robert George; Lewis, Patrick Raymond; Miller, James Edward et al.
Partner: UNT Libraries Government Documents Department

Real-time discriminatory sensors for water contamination events :LDRD 52595 final report.

Description: The gas-phase {mu}ChemLab{trademark} developed by Sandia can detect volatile organics and semi-volatiles organics via gas phase sampling . The goal of this three year Laboratory Directed Research and Development (LDRD) project was to adapt the components and concepts used by the {mu}ChemLab{trademark} system towards the analysis of water-borne chemicals of current concern. In essence, interfacing the gas-phase {mu}ChemLab{trademark} with water to bring the significant prior investment of Sandia and the advantages of microfabrication and portable analysis to a whole new world of important analytes. These include both chemical weapons agents and their hydrolysis products and disinfection by-products such as Trihalomethanes (THMs) and haloacetic acids (HAAs). THMs and HAAs are currently regulated by EPA due to health issues, yet water utilities do not have rapid on-site methods of detection that would allow them to adjust their processes quickly; protecting consumers, meeting water quality standards, and obeying regulations more easily and with greater confidence. This report documents the results, unique hardware and devices, and methods designed during the project toward the goal stated above. It also presents and discusses the portable field system to measure THMs developed in the course of this project.
Date: October 1, 2005
Creator: Borek, Theodore Thaddeus, III; Carrejo-Simpkins, Kimberly; Wheeler, David Roger; Adkins, Douglas Ray; Robinson, Alex Lockwood; Irwin, Adriane Nadine et al.
Partner: UNT Libraries Government Documents Department

Nanoporous-carbon adsorbers for chemical microsensors.

Description: Chemical microsensors rely on partitioning of airborne chemicals into films to collect and measure trace quantities of hazardous vapors. Polymer sensor coatings used today are typically slow to respond and difficult to apply reproducibly. The objective of this project was to produce a durable sensor coating material based on graphitic nanoporous-carbon (NPC), a new material first studied at Sandia, for collection and detection of volatile organic compounds (VOC), toxic industrial chemicals (TIC), chemical warfare agents (CWA) and nuclear processing precursors (NPP). Preliminary studies using NPC films on exploratory surface-acoustic-wave (SAW) devices and as a {micro}ChemLab membrane preconcentrator suggested that NPC may outperform existing, irreproducible coatings for SAW sensor and {micro}ChemLab preconcentrator applications. Success of this project will provide a strategic advantage to the development of a robust, manufacturable, highly-sensitive chemical microsensor for public health, industrial, and national security needs. We use pulsed-laser deposition to grow NPC films at room-temperature with negligible residual stress, and hence, can be deposited onto nearly any substrate material to any thickness. Controlled deposition yields reproducible NPC density, morphology, and porosity, without any discernable variation in surface chemistry. NPC coatings > 20 {micro}m thick with density < 5% that of graphite have been demonstrated. NPC can be 'doped' with nearly any metal during growth to provide further enhancements in analyte detection and selectivity. Optimized NPC-coated SAW devices were compared directly to commonly-used polymer coated SAWs for sensitivity to a variety of VOC, TIC, CWA and NPP. In every analyte, NPC outperforms each polymer coating by multiple orders-of-magnitude in detection sensitivity, with improvements ranging from 103 to 108 times greater detection sensitivity! NPC-coated SAW sensors appear capable of detecting most analytes tested to concentrations below parts-per-billion. In addition, the graphitic nature of NPC enables thermal stability > 600 C, several hundred degrees higher than the polymers. This ...
Date: November 1, 2004
Creator: Overmyer, Donald L.; Siegal, Michael P.; Staton, Alan W.; Provencio, Paula Polyak & Yelton, William Graham
Partner: UNT Libraries Government Documents Department

Advanced polychromator systems for remote chemical sensing (LDRD project 52575).

Description: The objective of this LDRD project was to develop a programmable diffraction grating fabricated in SUMMiT V{trademark}. Two types of grating elements (vertical and rotational) were designed and demonstrated. The vertical grating element utilized compound leveraged bending and the rotational grating element used vertical comb drive actuation. This work resulted in two technical advances and one patent application. Also a new optical configuration of the Polychromator was demonstrated. The new optical configuration improved the optical efficiency of the system without degrading any other aspect of the system. The new configuration also relaxes some constraint on the programmable diffraction grating.
Date: January 1, 2005
Creator: Sinclair, Michael B.; Pfeifer, Kent Bryant & Allen, James Joe
Partner: UNT Libraries Government Documents Department

A sensor management architecture concept for monitoring emissions from open-air demil operations.

Description: Sandia National Laboratories, CA proposed a sensor concept to detect emissions from open-burning/open-detonation (OB/OD) events. The system would serve two purposes: (1) Provide data to demilitarization operations about process efficiency, allowing process optimization for cleaner emissions and higher efficiency. (2) Provide data to regulators and neighboring communities about materials dispersing into the environment by OB/OD operations. The proposed sensor system uses instrument control hardware and data visualization software developed at Sandia National Laboratories to link together an array of sensors to monitor emissions from OB/OD events. The suite of sensors would consist of various physical and chemical detectors mounted on stationary or mobile platforms. The individual sensors would be wirelessly linked to one another and controlled through a central command center. Real-time data collection from the sensors, combined with integrated visualization of the data at the command center, would allow for feedback to the sensors to alter operational conditions to adjust for changing needs (i.e., moving plume position, increased spatial resolution, increased sensitivity). This report presents a systems study of the problem of implementing a sensor system for monitoring OB/OD emissions. The goal of this study was to gain a fuller understanding of the political, economic, and technical issues for developing and fielding this technology.
Date: September 1, 2005
Creator: Johnson, Michael M.; Robinson, Jerry D.; Stoddard, Mary Clare; Horn, Brent A.; Lipkin, Joel & Foltz, Greg W.
Partner: UNT Libraries Government Documents Department

Viral RNA testing and automation on the bead-based CBNE detection microsystem.

Description: We developed prototype chemistry for nucleic acid hybridization on our bead-based diagnostics platform and we established an automatable bead handling protocol capable of 50 part-per-billion (ppb) sensitivity. We are working towards a platform capable of parallel, rapid (10 minute), raw sample testing for orthogonal (in this case nucleic acid and immunoassays) identification of biological (and other) threats in a single sensor microsystem. In this LDRD we developed the nucleic acid chemistry required for nucleic acid hybridization. Our goal is to place a non-cell associated RNA virus (Bovine Viral Diarrhea, BVD) on the beads for raw sample testing. This key pre-requisite to showing orthogonality (nucleic acid measurements can be performed in parallel with immunoassay measurements). Orthogonal detection dramatically reduces false positives. We chose BVD because our collaborators (UC-Davis) can supply samples from persistently infected animals; and because proof-of-concept field testing can be performed with modification of the current technology platform at the UC Davis research station. Since BVD is a cattle-prone disease this research dovetails with earlier immunoassay work on Botulinum toxin simulant testing in raw milk samples. Demonstration of BVD RNA detection expands the repertoire of biological macromolecules that can be adapted to our bead-based detection. The resources of this late start LDRD were adequate to partially demonstrate the conjugation of the beads to the nucleic acids. It was never expected to be adequate for a full live virus test but to motivate that additional investment. In addition, we were able to reduce the LOD (Limit of Detection) for the botulinum toxin stimulant to 50 ppb from the earlier LOD of 1 ppm. A low LOD combined with orthogonal detection provides both low false negatives and low false positives. The logical follow-on steps to this LDRD research are to perform live virus identification as well as concurrent nucleic acid and ...
Date: September 1, 2008
Creator: Galambos, Paul C.; Bourdon, Christopher Jay; Farrell, Cara M.; Rossito, Paul (University of California at Davis); McClain, Jaime L.; Derzon, Mark Steven et al.
Partner: UNT Libraries Government Documents Department

Viral vectors for gene modification of plants as chem/bio sensors.

Description: Chemical or biological sensors that are specific, sensitive, and robust allowing intelligence gathering for verification of nuclear non-proliferation treaty compliance and detouring production of weapons of mass destruction are sorely needed. Although much progress has been made in the area of biosensors, improvements in sensor lifetime, robustness, and device packaging are required before these devices become widely used. Current chemical and biological detection and identification techniques require less-than-covert sample collection followed by transport to a laboratory for analysis. In addition to being expensive and time consuming, results can often be inconclusive due to compromised sample integrity during collection and transport. We report here a demonstration of a plant based sensor technology which utilizes mature and seedling plants as chemical sensors. One can envision genetically modifying native plants at a site of interest that can report the presence of specific toxins or chemicals. In this one year project we used a developed inducible expression system to show the feasibility of plant sensors. The vector was designed as a safe, non-infectious vector which could be used to invade, replicate, and introduce foreign genes into mature host plants that then allow the plant to sense chem/bio agents. The genes introduced through the vector included a reporter gene that encodes for green fluorescent protein (GFP) and a gene that encodes for a mammalian receptor that recognizes a chemical agent. Specifically, GFP was induced by the presence of 17-{beta}-Estradiol (estrogen). Detection of fluorescence indicated the presence of the target chemical agent. Since the sensor is a plant, costly device packaging development or manufacturing of the sensor were not required. Additionally, the biological recognition and reporting elements are maintained in a living, natural environment and therefore do not suffer from lifetime disadvantages typical of most biosensing platforms. Detection of the chem/bio agent reporter (GFP) can be ...
Date: November 1, 2006
Creator: Manginell, Monica; Harper, Jason C.; Arango, Dulce C.; Brozik, Susan Marie & Dolan, Patricia L.
Partner: UNT Libraries Government Documents Department

Microcalibrator system for chemical signature and reagent delivery.

Description: Networked systems of low-cost, small, integrable chemical sensors will enable monitoring of Nonproliferation and Materials Control targets and chemical weapons threats. Sandia-designed prototype chemical sensor systems are undergoing extended field testing supported by DOE and other government agencies. A required surety component will be verification of microanalytical system performance, which can be achieved by providing a programmable source of chemical signature(s) for autonomous calibration of analytical systems. In addition, such a controlled chemical source could be used to dispense microaliquots of derivatization reagents, extending the analysis capability of chemical sensors to a wider range of targets. We have developed a microfabricated system for controlled release of selected compounds (calibrants) into the analytical stream of microsensor systems. To minimize pumping and valve requirements of microfluidic systems, and to avoid degradation issues associated with storage of dilute solutions, we have utilized thermally labile organic salts as solid-phase reservoir materials. Reproducible deposition of tetrapropyl ammonium hydroxide onto arrays of microfabricated heating elements can provide a pair of calibration marker compounds (one fast and one slow-eluting compound) for GC analyses. The use of this microaliquot gas source array for hydrogen generation is currently under further development. The goal of the latter effort will be to provide a source of high-pressure, low viscosity GC carrier gas for Sandia's next-generation microfabricated gas-phase chemical analysis systems.
Date: March 1, 2005
Creator: Staton, Alan W.; Simonson, Robert Joseph; Adkins, Douglas Ray; Rawlinson, Kim Scott; Robinson, Alex Lockwood; Hance, Bradley G. et al.
Partner: UNT Libraries Government Documents Department

Self-Contained, Hand-held, Optical Waveguide, Chemical Sensor System

Description: A self-contained, hand-held, optical waveguide, chemical detection system has been built to detect and quantify gases and vapors. The system uses a hybrid integrated circuit (IC) containing optical waveguides coated with sensing chemistry as the optical platform. The IC with sensing chemistry is available commercially under the name Sensor-on-a-Chip. This IC is mounted in a small, uniquely designed sample chamber where the measured analyte is identified by the sensing chemistry and biochemistry. Continuous or stop-flow sampling is possible. Sensitivities in the low parts-per-million have been attained for hydrocarbons and alcohol. Analyte coverage is only limited by the sensing chemistries and biochemistries that are available.
Date: November 1, 1998
Creator: Pollina, R. J.
Partner: UNT Libraries Government Documents Department

Chemiresistor microsensors for in-situ monitoring of volatile organic compounds : final LDRD report.

Description: This report provides a summary of the three-year LDRD (Laboratory Directed Research and Development) project aimed at developing microchemical sensors for continuous, in-situ monitoring of volatile organic compounds. A chemiresistor sensor array was integrated with a unique, waterproof housing that allows the sensors to be operated in a variety of media including air, soil, and water. Numerous tests were performed to evaluate and improve the sensitivity, stability, and discriminatory capabilities of the chemiresistors. Field tests were conducted in California, Nevada, and New Mexico to further test and develop the sensors in actual environments within integrated monitoring systems. The field tests addressed issues regarding data acquisition, telemetry, power requirements, data processing, and other engineering requirements. Significant advances were made in the areas of polymer optimization, packaging, data analysis, discrimination, design, and information dissemination (e.g., real-time web posting of data; see www.sandia.gov/sensor). This project has stimulated significant interest among commercial and academic institutions. A CRADA (Cooperative Research and Development Agreement) was initiated in FY03 to investigate manufacturing methods, and a Work for Others contract was established between Sandia and Edwards Air Force Base for FY02-FY04. Funding was also obtained from DOE as part of their Advanced Monitoring Systems Initiative program from FY01 to FY03, and a DOE EMSP contract was awarded jointly to Sandia and INEEL for FY04-FY06. Contracts were also established for collaborative research with Brigham Young University to further evaluate, understand, and improve the performance of the chemiresistor sensors.
Date: September 1, 2003
Creator: Thomas, Michael Loren; Hughes, Robert Clark; Kooser, Ara S.; McGrath, Lucas K.; Ho, Clifford Kuofei; Wright, Jerome L. et al.
Partner: UNT Libraries Government Documents Department