Larry R. Senesac

Nanosensors for trace explosive detection

Selective and sensitive detection of explosives is very important in countering terrorist threats. Detecting trace explosives has become a very complex and expensive endeavor because of a number of factors, such as the wide variety of materials that can be used as explosives, the lack of easily detectable signatures, the vast number of avenues by which these weapons can be deployed, and the lack of inexpensive sensors with high sensitivity and selectivity. High sensitivity and selectivity, combined with the ability to lower the deployment cost of sensors using mass production, is essential in winning the war on explosives-based terrorism. Nanosensors have the potential to satisfy all the requirements for an effective platform for the trace detection of explosives.Selective and sensitive detection of explosives is very important in countering terrorist threats. Detecting trace explosives has become a very complex and expensive endeavor because of a number of factors, such as the wide variety of materials that can be used as explosives, the lack of easily detectable signatures, the vast number of avenues by which these weapons can be deployed, and the lack of inexpensive sensors with high sensitivity and selectivity. High sensitivity and selectivity, combined with the ability to lower the deployment cost of sensors using mass production, is essential in winning the war on explosives-based terrorism. Nanosensors have the potential to satisfy all the requirements for an effective platform for the trace detection of explosives.

Standoff photoacoustic spectroscopy

Here, we demonstrate a variation of photoacoustic spectroscopy that can be used for obtaining spectroscopic information of surface adsorbed chemicals in a standoff fashion. Pulsed light scattered from a target excites an acoustic resonator and the variation of the resonance amplitude as a function of illumination wavelength yields a representation of the absorption spectrum of the target. We report sensitive and selective detection of surface adsorbed compounds such as tributyl phosphate and residues of explosives such as trinitrotoluene at standoff distances ranging from 0.5–20m, with a detection limit on the order of 100ng∕cm2.

Trace Explosive Detection using Photothermal Deflection Spectroscopy

Satisfying the conditions of high sensitivity and high selectivity using portable sensors that are also reversible is a challenge. Miniature sensors such as microcantilevers offer high sensitivity but suffer from poor selectivity due to the lack of sufficiently selective receptors. Although many of the mass deployable spectroscopic techniques provide high selectivity, they do not have high sensitivity. Here, we show that this challenge can be overcome by combining photothermal spectroscopy on a bimaterial microcantilever with the mass induced change in the cantilever’s resonance frequency. Detection using adsorption-induced resonant frequency shift together with photothermal deflection spectroscopy shows extremely high selectivity with a subnanogram limit of detection for vapor phase adsorbed explosives, such as pentaerythritol tetranitrate (PETN), cyclotrimethylene trinitramine (RDX), and trinitrotoluene (TNT).

IR imaging using uncooled microcantilever detectors

Uncooled bimaterial microcantilever detectors were fabricated and used to obtain infrared (IR) images of objects at temperatures ranging from room temperature to a few hundred degrees C. Images were obtained using both single 50 micro m x 50 micro m microcantilever IR detectors and arrays of microcantilever detectors. Thermal radiation from the target object was imaged onto the detector and the resulting temperature change caused microcantilever bending due to the bimaterial effect. This micromechanical bending was measured using two different non-contact optical readout techniques and IR images were obtained. A smaller size (20 micro m x 20 micro m) microcantilever IR detector was also used to capture IR images of near room temperature objects.

Micro-differential thermal analysis detection of adsorbed explosive molecules using microfabricated bridges

Although micromechanical sensors enable chemical vapor sensing with unprecedented sensitivity using variations in mass and stress, obtaining chemical selectivity using the micromechanical response still remains as a crucial challenge. Chemoselectivity in vapor detection using immobilized selective layers that rely on weak chemical interactions provides only partial selectivity. Here we show that the very low thermal mass of micromechanical sensors can be used to produce unique responses that can be used for achieving chemical selectivity without losing sensitivity or reversibility. We demonstrate that this method is capable of differentiating explosive vapors from nonexplosives and is additionally capable of differentiating individual explosive vapors such as trinitrotoluene, pentaerythritol tetranitrate, and cyclotrimethylenetrinitromine. This method, based on a microfabricated bridge with a programmable heating rate, produces unique and reproducible thermal response patterns within 50 ms that are characteristic to classes of adsorbed explosive molecules. We demonstrate that this micro-differential thermal analysis technique can selectively detect explosives, providing a method for fast direct detection with a limit of detection of 600x10(-12) g.

10 mu m ethylene: spectroscopy, intensities and a planetary modeler's atlas

FTS and TDL spectra of ethylene in the 10 mum region have been observed, measured, calibrated, assigned and intensities have been measured. The ultimate goal of this work is the production of a planetary modelers atlas. A spectrum taken in double-pass configuration at the McMath-Pierce FTS instrument at Kitt Peak National Observatory has been frequency calibrated using CO2 laser bands. Results of a previous analysis (Cauuet et al., J Mol Spectrosc 1990;139:191) have enabled the assignment of the FTS spectrum wherein we have measured over 500 line intensities in the 900-1000 cm(-1) region. These FTS intensities have been calibrated against 13 isolated transitions, taken as secondary intensity standards. These standard lines have been measured independently using TDL (tunable-diode-laser) spectrometers at University of Tennessee and Goddard Space Flight Center. A calculated spectrum, including mixing coefficients for v(4), v(7), v(10) and v(12), and calculated relative intensities, and the TDL-calibrated FTS line intensities were used as data in a non-linear regression analysis to determine the 296 K vibrational band intensities of S-0-7(v) = 321.69 +/- 0.36 cm(-1)/cm atm, S-0-10(v) = 1.16 +/- 0.47 cm(-1)/cm atm, and S-0-12(v) = 31.60 +/- 9.80 cm(-1)/cm atm. These vibrational band intensities combined with the theoretical spectral-line atlas make possible the generation of an ethylene spectrum at an arbitrary temperature. Such spectra prove useful to the planetary-atmosphere modeling-community. A web site is available where an individual can interact with the model and download a custom atlas. The URL is http://aurora.phys.utk.edu/(similar to)blass/ethyatl/

Detection of adsorbed explosive molecules using thermal response of suspended microfabricated bridges

Here we present a thermophysical technique that is capable of differentiating vapor phase adsorbed explosives from nonexplosives and is additionally capable of differentiating individual species of common explosive vapors. This technique utilizes pairs of suspended microfabricated silicon bridges that can be heated in a controlled fashion. The differential thermal response of the bridges with and without adsorbed explosive vapor shows unique and reproducible characteristics depending on the nature of the adsorbed explosives. The tunable heating rate method described here is capable of providing unique signals for subnanogram quantities of adsorbed explosives within 50 ms.

Fabrication of quantum well microcantilever photon detectors

We have developed a new method for fabricating quantum well microcantilever arrays that can be used in a variety of sensing applications. Microcantilevers with quantum wells allow real-time manipulation of energy states using external stress thus providing photon wavelength tunability. For example, this can result in an effective and rapid change in electron energy levels in photon detection devices. We applied this microfabrication technique to develop InSb microcantilevers and small arrays of GaAs/GaA1As microcantilever quantum wells. Such arrays can be useful in the detection of infrared (IR) radiation at room temperature.

Piezoresistive cantilever array sensor for consolidated bioprocess monitoring

Cellulolytic microbes occur in diverse natural niches and are being screened for industrial modification and utility. A microbe for consolidated bioprocessing (CBP) development can rapidly degrade pure cellulose and then ferment the resulting sugars into fuels. To identify and screen for novel microbes for CBP, we have developed a piezoresistive cantilever array sensor which is capable of simultaneous monitoring of glucose and ethanol concentration changes in a phosphate buffer solution. 4-mercaptophenylboronic acid and polyethyleneglycol-thiol are employed to functionalize each piezoresistive cantilever for glucose and ethanol sensing, respectively. Successful concentration measurements of glucose and ethanol with minimal interferences are obtained with our cantilever array sensor.

Absolute intensities in the ν7 band of ethylene: tunable laser measurements used to calibrate FTS broadband spectra

Abstract Three independent measurements of ν7 ethylene transitions at two different laboratories yield direct determinations of absolute intensity for 13 transitions. The 13 intensities are used to calibrate the intensities of a broadband high-resolution 10 μm spectrum of ethylene taken at the McMath Solar Telescope FTS facility. The least-squares fitting of the FTS intensity observations to the precisely determined TDL intensities results in validation of the broadband data for which sample pressure and temperature were marginally known. This “calibration” of the FTS spectrum makes it possible to determine intensities of transitions in several bands in the 800–1100 cm−1 broadband FTS spectrum.