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Overview of organic nanofiber technology for trace detection of chemicals.
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B e n R o l l i n s9 2 5 . 7 0 5 . 1 2 2 5
b e n . r o l l i n s @ v a p o r s e n s . c o m
S M B B B u i l d i n g , R m 5 5 4 3
3 6 S o u t h W a s a t c h D r .
S a l t L a k e C i t y , U T 8 4 1 1 2
N a n o f i b e r S e n s o r s f o r
Tr a c e C h e m i c a l D e t e c t i o na d v a n c e s i n e l e c t r o n i c n o s e t e c h n o l o g y
Overview
Vaporsens is developing a novel, portable gas and vapor sampling device capable of detecting trace amounts of chemicals with greater sensitivity, accuracy, and speed than has been heretofore possible in such a small package. In short, it is an electronic nose.
Electronic noses have previously been researched and even commercialized, however, they have been limited by sensor lifetime, lack of sensitivity, and selectivity (when using conducting polymers), or by humidity, environmental effects, and selectivity (when using Nanotubes and Metal Oxide Nanowires). Vaporsens overcomes these limitations with its organic nanofiber technology.
Current Development Platform. The Technology Readiness Level of the device is
a 7 for industrial applications and a 5 for defense applications (on a scale of 1-9)
Platform Benefits
Small Size: Current desktop prototype is about the size of a matchbox and it can be shrunk further
Highly Sensitive: For trace amounts from the parts per million to parts per trillion range
Selective: Selective towards multiple chemicals as demonstrated in 30 publications
Rapid Response: Sensors respond immediately
Sample input: Ambient air, headspace, or process line
Replaceable Sensor: The sensor can be easily replaced as needed. Depending on the application the sensor may need replacement every 1-12 months
Low Power Requirements
No Radioactive Materials
A Nanofiber-based chemiresistor detection technology :
Trace Chemical DetectionThe Vaporsens sensor creates different signatures for different chemicals. Sensors are especially sensitive to redox active chemicals including: Amines, Nitros, Phosphines, Peroxides, Phenols, Ammonia, and other substances such as TICs, Chemical Agents, Pesticides, Explosives.
The sensor is not intended for Nuclear, Radiological, or Biological (directly, but potentially is capable of detecting the metabolites of organisms) targets and it is selective against these substances.
At this stage, the detector is to be used to alarm for the presence of trace chemicals rather than provide precise quantitative measurements.
The sensors demonstrate very good specificity between chemical classes and good specificity within a chemical class. It is ideal for
Detecting a chemical in the presence of a strong background Detecting a chemical out of complex mixture Monitoring an entire complex mixture.
A response signature or finger print for each compound is shown. A response signature results from the combination of the responses of the 8 fibers. The data shown is preprocessed for better classification. Each nanofiber sensor was exposed for 200 seconds. (FN is Fiber Number)
Chemicals detectedExplosives NitrosPeroxides
Tested to Date Nitromethane DNT (Dinitrotoluene) TNT (Trinitrotoluene) ANFO (Ammonium Nitrate
Fuel Oil) Ammonium Nitrate PETN (may detect taggant) RDX (may detect taggant) TATP (Triacetone
Triperoxide) H2O2 (Hydrogen Peroxide)
Amine Containing CompoundsTested to Date N-MethylPhenethylamine (Isomer of
Amphetamine/Methamphetamine analog)
Methylamine (Used in Synthesis of Methamphetamine)
Ammonia (Used in Synthesis of Methamphetamine)
Aniline Triethylamine Diethylamine
TICs - Toxic Industrial ChemicalsAcidsAcid PrecursorsPeroxides
Tested to Date: Cl2 (Chlorine Gas) NH3 (Ammonia) H2O2 (Hydrogen Peroxide) SO2 (Sulfur Dioxide) HCl (Hydrochloric Acid) TEP (Triethyl Phosphate) PH3 (Phosphine) HCN (Hydrogen Cyanide) Arsine Formaldehyde
VOCs Volatile Organic Compounds Benzaldehyde Hexane Acetone Ethanol Diesel Fuel Nitrobenzene Formaldehyde
CWAs - Chemical Warfare AgentsPhosphatesSulfidesPhosgene
Tested to Date: TEP (Triethylphosphate) DMMP (Dimethyl
methylphosphonate) ) (Sarin Analog)
2-Chloroethyl ethyl sulfide (Mustard Gas)
Triphosgene Methyl Salicylate
Food SafetyTCA (Trichloroanisole)*Melamine*Trimethylamine
Other chemicals within this class that are of interest
Potential ApplicationsPotential Applications: Trace Detector for Explosives, Chem Agents, Toxic Chemicals, Food Safety, Taints in Food and beverage, Gas Leaks, Pharmaceutical safety.
Quality AssuranceLaboratory device with greater
sensitivity to vapors than current equipment.
Handheld Point Detection Handheld detector roughly one-fourth the weight and one-half the size of the
current Ion Mobility Spectrometry (IMS) based portable systems. (NSF Funding)
Remotely Networked Monitors Remote detection of harmful chemicals. Low battery requirements result in long
lifetime. (DTRA Funding)
Wearable Monitor Lightweight wearable monitors for monitoring TICs or Chemical Agent
Devices.
Fixed Monitor For more robust, long-term monitors, stationary monitors with an external
power source can be developed.
Comparison to Other E-nose Technologies
Sensor Type MOS CP QCM SAW Nanofiber
Operating Temp C 300-400 Ambient Ambient Ambient Ambient
Sensitivity >0.1ppm 0.01ppm >0.1ppm ppb ppt
Selectivity Poor Moderate High High High
Reproducibility Poor Good Moderate Moderate Good
Temperature Drift Low High Moderate High Low
Humidity Drift Low High Low Low Low
Response time (s) 0.5-5 20-50 20-50 20-50 5-60
Recovery time Fast Slow Slow Slow Fast
Lifetime (years) 3 to 5 1 to 2
Comparison to Current Trace Technologies
Sen
siti
vity
Selectivity
Polymer FilmAFP
Portable GC/MS
PID
IMS
Nanofiber
Comparison to Current Trace Technologies
Port
abili
ty
Cost Effectiveness
Polymer FilmAFP
Portable GC/MS
PID
IMS
Nanofiber
Technology - Organic Nanofibers The detector is based on patented organic nanofiber sensors which were originally
developed at the University of Utah with funding from the Department of
Homeland Securitys Explosives Division.
Organic Nanofibers: Vaporsens sensor materials are organic nanofibers capable of
detecting trace amounts of target chemicals of interest. In brief, our nanofibers are
prepared from building block molecules (based on a perylene core molecule) with
unique side groups.
These building block molecules are then made to self-assemble into nanofibers by
manipulating parameters including solvent polarity and temperature. The
nanofibers can then be coated onto a substrate. Because the nanofibers are
conductive, when they are coated onto interdigitated electrodes (IDEs) they
complete an electrical circuit.
Technology Sensing Mechanism
The mechanism is a chemiresistor approach:
our sensor changes its electrical resistance in
response to changes in a nearby chemical
environment.
The nanofibers form a net or porous structure
with a large surface area that specifically
captures targeted molecules from the air
through molecular diffusion and surface
adsorption.
(A) SEM image of nanofibers coated on glass. (B) Nanofibers suspended in ethanol. (C) Interdigitated electrode. (D) Fibers coated onto
interdigitated electrode and wire bonded onto sensor board array. (E) Sensor board array plugs into electronic base.
BA C D E
When the nanofibers capture target molecules, they will either withdraw electrons from the chemical or donate electrons to itresulting in an increase or decrease in observed current. The response time for detection is then measured in seconds, not minutes.
Over thirty fibers have been developed to date. Each one responds differently to a chemical group. When the nanofiber sensors arecombined into an array, their combined responses form a unique signature pattern or smell-print for each chemical. Furthermore, an essentially unlimited number of nanofibers can be developed leading to further improved selectivity for a broader range of target analytes.
BackgroundThe sensor technology originated from research funded by previous Homeland Security and National Science Foundation grants in support of Dr. Ling Zangs work on sensory nanomaterials at the University of Utah, which has generated over 30 peer-reviewed publications and 10 patents.
Vaporsens was incorporated in 2011 to commercialize this sensor technology and has received external seed funding from private investors. In 2013, DOD-DTRA awarded Vaporsens $1.4M (via subcontract) to develop the sensory materials into remotely networked chemical vapor sensors. In 2014, the NSF awarded Vaporsens a Phase II SBIR to develop a handheld explosives vapor detector. Vaporsens now has 6 full-time employees and 2 part time. Key personnel include:
Ben Rollins, Project Manager: Entrepreneur and project manager now leading his second technology transfer startup.
Dr. Ling Zang, CSO and Advisor: Research on sensory nanomaterials has resulted in over 30 peer-reviewed publications and 10 patents.
Paul Slattum, Sr. Chemist: An author of 11 papers and inventor on 11 patents. Over 20 years of industrial experience in organic chemistry.
Dr. Yin Sun, PI: Analytical chemist with over 16 years in the trace detection and instrumentation industry. Authored two books on trace detection. Led developments at Smiths Detection and Spectrafluidcs.
Paul Allen, Sr. Engineer: Electrical, Mechanical, Industrial engineer with experience in startups and new products
Dr. Greger Andersson, Principal Scientist, Data Analytics: Brings over 20 years of experience working on chemometrics for various technologies including IMS and Metal Oxide Sensors.
Patents and Selected PublicationsPatent Status IP Type Number
Perylene Nanofiber Fluorescent Sensor for Highly Sensitive and Selective Sensing of Amines
Issued U.S. Patent No. 8,486,708 B2
Photoconductive sensor materials for detection of explosive vapor Issued U.S. Patent No. 8,889,420
Optoelectrical vapor sensing Issued U.S. Patent No. 8,703,500
Fluorescent Carbazole Oligomers Nanofibril Materials for Vapor Sensing Issued U.S. Patent No. 8,809,063
Fluorescent Sensing of Vapors Using Tubular Nanofibril Materials PublishedPublication numberWO2013066458 A3
Multimode platform for detection of compounds Published Publication number WO2013095730
Selected Publications
Diffusion-Controlled Detection of Trinitrotoluene: Interior Nanoporous Structure and Low Highest Occupied Molecular Orbital Level of Building Blocks Enhance Selectivity and Sensitivity, Che et al., Journal of the American Chemical Society 2012 134 (10), 4978-4982, DOI: 10.1021/ja300306e
Organic Optoelectronic Materials for Trace Explosive Sensing, Zhan et al.
Ambient photodoping of p-type organic nanofibers: highly efficient photoswitching and electrical vapor sensing of amines, Che et al., Chem. Commun., 2010,46, 4127-4129, DOI: 10.1039/C0CC00823K
Ultrathin n-Type Organic Nanoribbons with High Photoconductivity and Application in Optoelectronic Vapor Sensing of Explosives, Che et al., Journal of the American Chemical Society 2010 132 (16), 5743-5750, DOI: 10.1021/ja909797q
One-Dimensional Self-Assembly of Planar -Conjugated Molecules: Adaptable Building Blocks for Organic Nanodevices, Zang et al., Accounts of Chemical Research 2008 41 (12), 1596-1608, DOI: 10.1021/ar800030w
Expedient Vapor Probing of Organic Amines Using Fluorescent Nanofibers Fabricated from an n-Type Organic Semiconductor, Che et al., Nano Letters 2008 8 (8), 2219-2223 DOI: 10.1021/nl080761g
Sensor CharacteristicsThe following slides represent a few of the characteristics of the nanofiber sensor.
Sensitivity
Chemical Class
Chemical AgentVaporsens Preliminary Limit
of Detection (ppm) Critical
Concentration 1Negligible
Concentrations 1
Based on a 30 seconds exposure to analyte
Military Requires Detection within 30 Seconds
Military Requires Detection within 180
Seconds
NerveSarin Simulant (GB) - Dimethyl methyl phosphonate(DMMP)
0.018 0.043 0.001
BlisterMustard Gas Simulant (HD) - 2-Chloroethyl ethyl sulfide
0.650 0.4900 0.0785
TIC Ammonia (NH3) 0.016 2732.65 30.2
Sulfur Dioxide (S02) 0.019 30.18 0.2
Phosgene 0.020 3.71 0.099
Chlorine 0.0003 51.65 0.52
Hydrogen Cyanide (CK) 0.021 9.06 0.68
All numbers in ppm
1 Aberdeen Proving Ground, MD; Performance Specifications for the Next Generation Chemical Detector, 2013
Results from preliminary sensitivity testing of toxic chemicals and chemical warfare agents simulants. Current prototype meets or exceeds military requirements.
Selectivity
PCA analysis to show that these chemical compounds can be separated.
Interferent DMMP/AcetoneBackground interferents have little affect on the nanofiber response to an analyte. This test shows the nanofiber sensor arrays response to 9 ppm of DMMP (a common toxic chemical) in the presence of increasing concentrations of Acetone (0, 2 ppth, 13 ppth, 78 ppth) Although the amount DMMP is orders of magnitude less than the acetone, the fibers response to DMMP is nearly identical. Nearly 4 orders of magnitude!
8 Channel Sensor Array Responses to DMMP over time
Signature Similarity Scores
Acetone Concentration 0%1%
(3ppth)5%
(13ppth)30%
(78ppth)
Measured 94% 98% 99% 94%
Corrected 99.8% 99.6% 99.7% 99.7%
8 Channel Sensor Arrays Normalized Responses to DMMP in Increasing Levels of Acetone
Raw Data: Average relative response of sensors over 60 seconds. 4 different interferent levels.
Processed Data: Decomposed data from model tool
Two different 3 minute exposures to 9 ppm of DMMP at 10 minutes and again at 23 minutes
Interferent DMMP/HexaneThis test shows the nanofiber sensor arrays response to 9 ppm of DMMP (a common toxic chemical) in the presence of increasing concentrations of Hexane (0, 1 ppth, 7 ppth, 39 ppth) Although the amount DMMP is orders of magnitude less than the Hexane, the fibers response to DMMP is nearly identical.
Two different 3 minute exposures to DMMP at 10 minutes and again at 23 minutes
Signature Similarity Scores
Hexane Concentration 0% 1% 5% 30%
Measured 94% 99% 99% 95%
Corrected 99.7% 99.9% 99.7% 99.9%
8 Channel Sensor Arrays Normalized Responses to DMMP in Increasing Levels of Hexane
Raw Data: Average relative response of sensors over 60 seconds. 4 different interferent levels.
Processed Data: Decomposed data from model tool
8 Channel Sensor Array Responses to DMMP over time
Temperature Effect - DMMPBackground temperature has little affect on the nanofiber response to an analyte. This test shows the nanofiber sensor arrays response to 9 ppm of DMMP in the presence of temperature levels (2 C, 26 C, 35 C, 42 C). The fibers response to DMMP is very similar over different temperatures.
Signature Similarity Scores
Temperature 2 C 26 C 35 C 42 C
Measured 95% 97% 99% 94%
Corrected 99.5% 99.6% 99.9% 98.9%
8 Channel Sensor Arrays Normalized Responses to DMMP at Different Temperatures
Raw Data: Average relative response of sensors over 60 seconds to varying temperatures.
Processed Data: Decomposed data from model tool
Two different 3 minute exposures to DMMP at 10 minutes and again at 23 minutes
8 Channel Sensor Array Responses to DMMP over time
Humidity Effect - DMMPThe following demonstrates the humidity effect on the nanofiber responses to an analyte. This test shows the nanofiber sensor arrays response to 9 ppm of DMMP in the presence of increasing humidity levels (10%, 35%, 50%). The fibers response to DMMP is very similar over different humidity.
(Raw Data) (Corrected Data)
Signature Similarity Scores
Relative Humidity 10% 35% 50%
Measured 98% 98% 96%
Corrected 99.8% 99.7% 99.6%
8 Channel Sensor Arrays Normalized Responses to DMMP at Different Humidity Levels
Raw Data: Average relative response of sensors over 60 seconds to varying humidity levels (at 42 C / 107 F).
Processed Data: Decomposed data from model tool
Two different 3 minute exposures to DMMP at 10 minutes and again at 23 minutes
8 Channel Sensor Array Responses to DMMP over time