We demonstrate the rapid detection of explosive vapors based on a fiber-based optical Fabry-Pérot (FP) gas sensor. The
sensing probe of the FP sensor is composed of a thin metal layer and a vapor-sensitive polymer layer that are deposited
sequentially on a cleaved fiber endface to form an FP cavity. The interference spectrum generated from the reflected
light at the metal-polymer and polymer-air interfaces changes upon the absorption of gas analyte. By monitoring the
interference shift, we are able to obtain quantitative and knetic information of the interaction between the analyte and the
polymer layer. We further assemble the FP sensor with a short fused silica capillary into a sensor module, and employ it
in a gas chromotgraphy (GC) system for selevtive rapid on-column detection. In this report, we specifically target 2, 4-
dinitrotoluene (DNT) and 2, 4, 6-trinitrotoluene (TNT) for their obvious defense applications. This work could lead to a
portable sensor capable of detecting low concentrations of DNT, TNT, and other explosive chemicals.
A versatile, compact, and sensitive fiber-based optical Fabry-Pérot (FP) gas sensor is reported in this paper. The sensor
probe is composed of a silver layer and a vapor-sensitive polymer layer that are deposited on the cleaved fiber endface to
form an FP cavity sequentially. The interference spectrum generated from the reflected light at the silver-polymer and
polymer-air interfaces changes upon the absorption of gas analytes. This structure enables using polymer of any
refractive index (RI) as the sensing layer, which significantly enhances the sensor versatility. Two polymers of
polyethylene glycol (PEG) 400 (RI=1.465-1.469) and Norland Optical Adhesive (NOA) 81 (RI=1.53-1.56) are used as
the gas sensing polymer to demonstrate the feasibility of the FP sensor, and show drastically different sensor response to
various gas analytes. In addition, we assemble the FP sensor with a short fused silica capillary into a sensor module, and
employ it in the gas chromotgraphy (GC) system to investigate its capability as a GC detector for rapid on-column
detection.
We develop a novel chemical vapor sensing platform based on optofluidic ring resonator (OFRR) for rapid and on-column
detection and analysis of a wide range of chemical vapors. The OFRR is a thin-walled fused-silica capillary with
a diameter of ~100 μm and a few centimeters in length. The circular cross-section of the OFRR defines a ring resonator
that supports high-Q (>106) whispering gallery modes or circulating waveguide modes (WGMs). Polymer thin film is
coated on the OFRR capillary interior surface as a vapor sensitive material. The unique structure of the OFRR achieves
dual-use of the capillary as the gas delivery channel and as the sensing transducer, avoiding the necessity of building
extra gas detection chambers commonly seen in chemical vapor sensors. When vapor molecules pass through the OFRR,
the interaction between vapor molecules and the polymer causes polymer refractive index and thickness to change,
which leads to a WGM spectral shift. Therefore, by monitoring the WGMs spectrum in time, the quantitative and kinetic
information regarding vapor molecule-polymer interaction is acquired. The rapid detection of methanol and hexane
vapors representing polar and nonpolar analytes respectively are demonstrated with OFRR vapor sensors. Owing to the
unique multipoint on-column detection capability, the OFRR vapor sensor is studied for the development of the micro-
GC gas analyzer. Efficient separation and rapid detection are achieved by a few centimeters long OFRR capillary coated
with a stationary phase polymer. We further explore the capability of OFRR micro-GC for more challenging explosive
detection. The OFRR vapor sensing platform is a promising candidate for the development of rapid, sensitive, simple,
portable, and cost-effective micro-gas sensors.
A reactive chromophore developed at MIT exhibits sensitive and selective detection of surrogates for G-class nerve agents. This reporter acts by reacting with the agent to form an intermediate that goes through an internal cyclization reaction. The reaction locks the molecule into a form that provides a strong fluorescent signal. Using a fluorescent sensor platform, Nomadics has demonstrated rapid and sensitive detection of reactive simulants such as diethyl chloro-phosphate (simulant for sarin, soman, and related agents) and diethyl cyanophosphate (simulant for tabun). Since the unreacted chromophore does not fluoresce at the excitation wavelength used for the cyclized reporter, the onset of fluo-rescence can be easily detected. This fluorescence-based detection method provides very high sensitivity and could enable rapid detection at permissible exposure levels. Tests with potential interferents show that the reporter is very selective, with responses from only a few highly toxic, electrophilic chemicals such as phosgene, thionyl chloride, and strong acids such as HF, HCl, and nitric acid. Dimethyl methyl phosphonate (DMMP), a common and inactive simu-lant for other CW detectors, is not reactive enough to generate a signal. The unique selectivity to chemical reactivity means that a highly toxic and hazardous chemical is present when the reporter responds and illustrates that this sensor can provide very low false alarm rates. Current efforts focus on demonstrating the sensitivity and range of agents and toxic industrial chemicals detected with this reporter as well as developing additional fluorescent reporters for a range of chemical reactivity classes. The goal is to produce a hand-held sensor that can sensitively detect a broad range of chemical warfare agent and toxic industrial chemical threats.
There is a renewed interest in the development of chemical and biological agent sensors due to the increased threat of weapons deployment by terrorist organizations and rogue states. Optically based sensors address the needs of military and homeland security forces in that they are reliable, rapidly deployed, and can provide continuous monitoring with little to no operator involvement. Nomadics has developed optically based chemical weapons sensors that utilize reactive fluorescent chromophores initially developed by Professor Tim Swager at MIT. The chromophores provide unprecedented sensitivity and selectivity toward toxic industrial chemicals and certain chemical weapon agents. The selectivity is based upon the reactivity of the G-class nerve agents (phosphorylation of acetylcholinesterase enzyme) that makes them toxic. Because the sensor recognizes the reactivity of strong electrophiles and not molecular weight, chemical affinity or ionizability, our system detects a specific class of reactive agents and will be able to detect newly developed or modified agents that are not currently known. We have recently extended this work to pursue a combined chemical/biological agent sensor system incorporating technologies based upon novel deep ultraviolet (UV) light emitting diodes (LEDs) developed out of the DARPA Semiconductor UV Optical Sources (SUVOS) program.
A new sensor for highly toxic species including chemical warfare (CW) agents has been developed. This sensor is based on a unique CW indicating chromophore (CWIC) developed by Professor Tim Swager at MIT. The CWIC was designed to be sensitive to the reactivity that makes these chemicals so toxic. Since it requires the reactivity of the agent to be detected, the CWIC technology has shown remarkable selectivity for nerve agent surrogates and some other highly toxic species, thereby demonstrating the potential to provide low false alarm rate detection. Since the chromophore has mini-mal fluorescence prior to reaction with an electrophilic and toxic chemical, the sensor acts in a dark field fluorescence mode. This provides the sensor with exceptional sensitivity and a potential to detect priority analytes well below levels detected by current hand held sensors. Finally, it is based on a simple optical detection scheme that enables small and rugged sensors to be developed and produced at a low enough cost so they can be widely utilized.
Rapid detection and identification of bacteria and other pathogens is important for many civilian and military applications. The profiles of biological markers such as fatty acids can be used to characterize biological samples or to distinguish bacteria at the gram-type, genera, and even species level. Common methods for whole cell bacterial analysis are neither portable nor rapid, requiring lengthy, labor intensive sample preparation and bench-scale instrumentation. These methods chemically derivatize fatty acids to produce more volatile fatty acid methyl esters (FAMEs) that can be separated and analyzed by a gas chromatograph (GC)/mass spectrometer. More recent publications demonstrate decreased sample preparation time with in situ derivatization of whole bacterial samples using pyrolysis/derivatization. Ongoing development of miniaturized pyrolysis/GC instrumentation by this department capitalizes on Sandia advances in the field of microfabricated chemical analysis systems ((mu) ChemLab). Microdevices include rapidly heated stages capable of pyrolysis or sample concentration, gas chromatography columns, and surface acoustic wave (SAW) sensor arrays. We will present results demonstrating the capabilities of these devices toward fulfilling the goal of portable, rapid detection and early warning of the presence of pathogens in air or water.
Identification of bacteria and other biological moieties finds a broad range of applications in the environmental, biomedical, agricultural, industrial, and military arenas. Linking these applications are biological markers such as fatty acids, whose mass spectral profiles can be used to characterize biological samples and to distinguish bacteria at the gram-type, genera, and even species level. Common methods of sample analysis require sample preparation that is both lengthy and labor intensive, especially for whole cell bacteria. The background technique relied on here utilizes chemical derivatization of fatty acids to the more volatile fatty acid methyl esters (FAMEs), which can be separated on a gas chromatograph column or input directly into a mass spectrometer. More recent publications demonstrate improved sample preparation time with in situ derivatization of whole bacterial samples using pyrolysis at the inlet; although much faster than traditional techniques, these systems still rely on bench-top analytical equipment and individual sample preparation. Development of a miniaturized pyrolysis/GC instrument by this group is intended to realize the benefits of FAME identification of bacteria and other biological samples while further facilitating sample handling and instrument portability. The technologies being fabricated and tested have the potential of achieving pyrolysis and FAME separation on a very small scale, with rapid detection time (1-10 min from introduction to result), and with a modular sample inlet. Performance results and sensor characterization will be presented for the first phase of instrument development, encompassing the microfabricated pyrolysis and gas chromatograph elements.
KEYWORDS: Chromatography, Diffusion, Computer simulations, Chemical analysis, Data modeling, Coating, Chemical detection, Etching, Silicon, Microsystems
The gas chromatography (GC) column is a critical component in the microsystem for chemical detection ((mu) ChemLabTM) being developed at Sandia. The goal is to etch a `meter-long' GC column onto a 1-cm2 silicon chip while maintaining good chromatographic performance. Our design strategy is to use modeling and simulation approach. We have developed an analytical tool that models the transport and surface interaction process to achieve an optimized design of the GC column. This analytical tool has a flow module and a separation module. The flow module considers both the compressibility and slip flow effects that may significantly influence the gas transport in a long and narrow column. The separation module models analyte transport and physico-chemical interaction with the coated surface in the GC column. It predicts the column efficiency and performance. Results of our analysis will be presented in this paper.
The ability to characterize suspect facilities for intelligence or counterforce purposes will rely heavily on the ability to identify chemical effluents from such facilities. Sandia is developing a complete micro-scale chemical analysis system named (mu) ChemLabTM. This system will be extremely small and low power because of the utilization of integrated circuit fabrication techniques. The use of monolithic integration of such components as chemical preconcentration, separation, and detection, along with the eventual integration of micromachined pumps and valves, will not only lead to a dramatic size reduction, but also lead to the dramatic cost reduction that has been realized with monolithic integration of electronics. It will become practical to deploy large numbers of unattended chemical analysis systems for sensing low concentration effluents at high priority targets. (mu) ChemLabTM uses an array of serial and parallel separations channels (columns), each of which separates compounds on the basis of different `orthogonal' chemical properties, followed by highly sensitive detection techniques: laser-induced fluorescence in the liquid phase and arrays of acoustic wave devices in the gas phase. This array of separations will create a characteristic, highly specific signature for a acoustic wave devices in the gas phase. This array of separations will create a characteristic, highly specific signature for a compound. Identification of target species based on the combined results of multiple separations will have an extremely low false alarm rate because each separation is statistically independent. Because the separations will be run simultaneously in microchannels, analyses times are on the order of a few minutes. The necessary sample handling and detection systems will be implemented using microfabricated electronic, optical and fluidic components.
Liquid flow cells have been fabricated to prepare an array of QCMs operating simultaneously for detection and identification of VOCs in water. Two signals, a frequency response and a damping voltage response, were obtained per resonator. A blank QCM was used as a reference to account for changes in liquid density and viscosity. Nine different polymer coatings applied using a spin coat technique have been examined for VOC response under liquid flow conditions. A matrix of three classes of VOCs were examined for each coating with four chemicals in each class. The three classes of VOCs are polar, nonpolar and chlorinated. A pattern recognition technique, called visually empirical region of influence, was used to cluster the responses in n- dimensional space. Chemicals within a class varying by only one methyl group (e.g., toluene and xylene) are easily discriminated using only two different coatings with three different QCM responses. All chemicals were easily separated and detected with a total of 5 films and 6 responses with >99% accuracy.
High sensitivity acoustic wave chemical microsensors are being developed on GaAs substrates. These devices take advantage of the piezoelectric properties of GaAs as well as its mature microelectronics fabrication technology and nascent micromachining technology. The design, fabrication, and response of GaAs SAW chemical microsensors are reported. Functional integrated GaAs SAW oscillators, suitable for chemical sensing, have been produced. The integrated oscillator requires 20 mA at 3 VDC, operates at frequencies up to 500 MHz, and occupies approximately 2 mm2. Discrete GaAs sensor components, including IC amplifiers, SAW delay lines, and IC phase comparators have been fabricated and tested. A temperature compensation scheme has been developed that overcomes the large temperature dependence of GaAs acoustic wave devices. Packaging issues related to bonding miniature flow channels directly to the GaAs substrates have been resolved. Micromachining techniques for fabricating FPW and TSM microsensors on thin GaAs membranes are presented and GaAs FPW delay line performance is described. These devices have potentially higher sensitivity than existing GaAs and quartz SAW sensors.
Using both wet and plasma etching, we have fabricated micro- channels in silicon substrates suitable for use as gas chromatography (GC) columns. Micro-channel dimensions range from 10 to 80 micrometer wide, 200 to 400 micrometer deep, and 10 cm to 100 cm long. Micro-channels 100 cm long take up as little as 1 cm2 on the substrate when fabricated with a high aspect ratio silicon etch (HARSE) process. Channels are sealed by anodically bonding Pyrex lids to the Si substrates. We have studied micro-channel flow characteristics to establish model parameters for system optimization. We have also coated these micro-channels with stationary phases and demonstrated GC separations. We believe separation performance can be improved by increasing stationary phase coating uniformity through micro-channel surface treatment prior to stationary phase deposition. To this end, we have developed microfabrication techniques to etch through silicon wafers using the HARSE process. Etching completely through the Si substrate facilitates the treatment and characterization of the micro-channel sidewalls, which dominate the GC physico- chemical interaction. With this approach, we separately treat the Pyrex lid surfaces that form the top and bottom surfaces of the GC flow channel.
Deep-reactive ion etching (DRIE) of silicon, also known as high-aspect-ratio silicon etching (HARSE), is distinguished by fast etch rates (approximately 3 micrometer/min), crystal orientation independence, anisotropy, vertical sidewall profiles and CMOS compatibility. By using through-wafer HARSE and stopping on a dielectric film placed on the opposite side of the wafer, freestanding dielectric membranes were produced. Dielectric membrane-based sensors and actuators fabricated in this way include microhotplates, flow sensors, valves and magnetically-actuated flexural plate wave (FPW) devices. Unfortunately, low-stress silicon nitride, a common membrane material, has an appreciable DRI etch rate. To overcome this problem HARSE can be followed by a brief wet chemical etch. This approach has been demonstrated using KOH or HF/Nitric/Acetic etchants, both of which have significantly smaller etch rates on silicon nitride than does DRIE. Composite membranes consisting of silicon dioxide and silicon nitride layers are also under evaluation due to the higher DRIE selectivity to silicon dioxide.
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