Nanoporous-carbon adsorbers for chemical microsensors.

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 superior thermal stability will enable higher-Temperature preconcentrator operation, as well as greatly prolonged device reliability, since polymers tend to degrade with time and repeated thermal cycling

Dissecting the molecular diversity and commonality of bovine and human treponemes identifies key survival and adhesion mechanisms

Here, we report the first complete genomes of three cultivable treponeme species from bovine digital dermatitis (DD) skin lesions, two comparative human treponemes and a bovine gastrointestinal (GI) isolate. Key genomic differences between bovine and human treponemes implicate microbial mechanisms that enhance knowledge of how DD, a severe disease of ruminants, has emerged into a prolific, worldwide disease. Bovine DD treponemes have additional oxidative stress genes compared to nearest human-isolated relatives, suggesting better oxidative stress tolerance, and potentially explaining how bovine strains can colonize skin surfaces. Comparison of both bovine DD and GI treponemes as well as bovine pathogenic and human non-pathogenic saprophyte Treponema phagedenis strains indicates genes encoding a five-enzyme biosynthetic pathway for production of 2,3-diacetamido-2,3-dideoxy-d-mannuronic acid, a rare di-N-acetylated mannuronic acid sugar as important for pathogenesis. Bovine T. phagedenis strains further differed from human strains by having unique genetic clusters including components of a type IV secretion system and a phosphate utilisation system including phoU, a gene associated with osmotic stress survival. Proteomic analyses confirmed bovine derived T. phagedenis exhibits expression of PhoU but not the putative secretion system whilst the novel mannuronic acid pathway was expressed in near entirety across the DD treponemes. Analysis of osmotic stress response in water identified a difference between bovine and human T. phagedenis with bovine strains surviving better. This novel mechanism could enable a selective advantage, allowing environmental persistence and transmission of bovine T. phagedenis. Finally, we investigated putative outer membrane protein (OMP) ortholog families across the DD treponemes and identified several families as multi-specific adhesins capable of binding extra cellular matrix (ECM) components. One bovine pathogen specific adhesin ortholog family showed considerable serodiagnostic potential with the Treponema medium representative demonstrating considerable disease specificity (91.6%). This work has shed light on treponeme host adaptation and has identified candidate molecules for future diagnostics, vaccination and therapeutic intervention

Microcalibrator system for chemical signature and reagent delivery.

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

µChemLab: twenty years of developing CBRNE detection systems with low false alarm rates

Gas Chromatography (GC) is routinely used in the laboratory to temporally separate chemical mixtures into their constituent components for improved chemical identification. This paper will provide a overview of more than twenty years of development of one-dimensional field-portable micro GC systems, highlighting key experimental results that illustrate how a reduction in false alarm rate (FAR) is achieved in real-world environments. Significantly, we will also present recent results on a micro two-dimensional GC (micro GCxGC) technology. This ultra-small system consists of microfabricated columns, NanoElectroMechanical System (NEMS) cantilever resonators for detection, and a valve-based stop-flow modulator. The separation of a 29-component polar mixture in less than 7 seconds is demonstrated along with peak widths in the second dimension ranging from 10-60 ms. For this system, a peak capacity of just over 300 was calculated for separation in about 6 s. This work has important implications for field detection, to drastically reduce FAR and significantly improve chemical selectivity and identification. This separation performance was demonstrated with the NEMS resonator and bench scale FID. But other detectors, suitably fast and sensitive can work as well. Recent research has shown that the identification power of GCxGC-FID can match that of GC-MS. This result indicates a path to improved size, weight, power, and performance in micro GCxGC systems outfitted with relatively non-specific, lightweight detectors. We will briefly discuss the performance of possible options, such as the pulsed discharge helium ionization detector (PDHID) and miniature correlation ion mobility spectrometer (mini-CIMS)

Viscoelastic coupling of nanoelectromechanical resonators.

This report summarizes work to date on a new collaboration between Sandia National Laboratories and the California Institute of Technology (Caltech) to utilize nanoelectromechanical resonators designed at Caltech as platforms to measure the mechanical properties of polymeric materials at length scales on the order of 10-50 nm. Caltech has succeeded in reproducibly building cantilever resonators having major dimensions on the order of 2-5 microns. These devices are fabricated in pairs, with free ends separated by reproducible gaps having dimensions on the order of 10-50 nm. By controlled placement of materials that bridge the very small gap between resonators, the mechanical devices become coupled through the test material, and the transmission of energy between the devices can be monitored. This should allow for measurements of viscoelastic properties of polymeric materials at high frequency over short distances. Our work to date has been directed toward establishing this measurement capability at Sandia

Mass-Transport-Limited Electrodeposition of High-Surface-Area Coatings for Surface Acoustic Wave Sensor Technology

The sensitivity of surface acoustic wave (SAW) sensors has been enhanced by increasing the active surface area of these devices. Electrodepositions of Ni, Pd, and Pt in a mass-transport-limited mode with trace foreign metals yield highly dendritic crystal structures of uniform macroscopic thickness. The concentration of metal ions, supporting electrolyte, agitation, and additives greatly impact the crystal morphology of the deposit. This methodology can be used simply and economically to provide high-area films in selective regions

Light clustering for dynamic image based lighting

High Dynamic Range (HDR) imagery has made it possible to relight virtual objects accurately with the captured lighting. This technique, called Image Based Lighting (IBL), is a commonly used to render scenes using real-world illumination. IBL has mostly been limited to static scenes due to limitations of HDR capture. However, recently there has been progress on developing devices which can capture HDR video sequences. These can be also be used to light virtual environments dynamically. If existing IBL algorithms are applied to this dynamic problem, temporal artifacts viewed as flickering can often arise due to samples being selected from different parts of the environment in consecutive frames. In this paper we present a method for efficiently rendering virtual scenarios with such captured sequences based on spatial and temporal clustering. Our proposed Dynamic IBL (DIBL) method improves temporal quality by suppressing flickering, and we demonstrate the application to fast previews of scenes lit by video environment maps