Chemiresistor Devices for Chemical Warfare Agent Detection Based on Polymer Wrapped Single-Walled Carbon Nanotubes

Chemical warfare agents (CWA) continue to present a threat to civilian populations and military personnel in operational areas all over the world. Reliable measurements of CWAs are critical to contamination detection, avoidance, and remediation. The current deployed systems in United States and foreign militaries, as well as those in the private sector offer accurate detection of CWAs, but are still limited by size, portability and fabrication cost. Herein, we report a chemiresistive CWA sensor using single-walled carbon nanotubes (SWCNTs) wrapped with poly(3,4-ethylenedioxythiophene) (PEDOT) derivatives. We demonstrate that a pendant hexafluoroisopropanol group on the polymer that enhances sensitivity to a nerve agent mimic, dimethyl methylphosphonate, in both nitrogen and air environments to concentrations as low as 5 ppm and 11 ppm, respectively. Additionally, these PEDOT/SWCNT derivative sensor systems experience negligible device performance over the course of two weeks under ambient conditions.

[1]  Ullrich Scherf,et al.  Conjugated polymer-assisted dispersion of single-wall carbon nanotubes: the power of polymer wrapping. , 2014, Accounts of chemical research.

[2]  Cheryl Surman,et al.  Materials and transducers toward selective wireless gas sensing. , 2011, Chemical reviews.

[3]  Douglas R. Kauffman,et al.  Carbon nanotube gas and vapor sensors. , 2008, Angewandte Chemie.

[4]  Jonathan N. Coleman,et al.  New Solvents for Nanotubes: Approaching the Dispersibility of Surfactants , 2010 .

[5]  Alexander Star,et al.  Electronic Detection of Specific Protein Binding Using Nanotube FET Devices , 2003 .

[6]  Akshay M. Phulgirkar,et al.  Flexible, all-organic chemiresistor for detecting chemically aggressive vapors. , 2012, Journal of the American Chemical Society.

[7]  Jay W. Grate.  Hydrogen‐Bond Acidic Polymers for Chemical Vapor Sensing , 2008 .

[8]  Richard D. McCullough,et al.  Effects of Structural Regularity on the Properties of Poly(3-alkylthienylenevinylenes) , 2000 .

[9]  Tsutomu Yokozawa,et al.  Chain-growth condensation polymerization for the synthesis of well-defined condensation polymers and pi-conjugated polymers. , 2009, Chemical reviews.

[10]  Darin W. Laird,et al.  Chain Growth Mechanism for Regioregular Nickel-Initiated Cross-Coupling Polymerizations , 2004 .

[11]  J. Fraser Stoddart,et al.  Preparation and Properties of Polymer-Wrapped Single-Walled Carbon Nanotubes , 2001 .

[12]  M. Prato,et al.  Organic functionalization of carbon nanotubes. , 2002, Journal of the American Chemical Society.

[13]  James Geoghegan,et al.  Chemical warfare agents , 2006 .

[14]  K. Mirica,et al.  Mechanical drawing of gas sensors on paper. , 2012, Angewandte Chemie.

[15]  T. Swager,et al.  Emerging Applications of Carbon Nanotubes , 2011 .

[16]  Lei Zhang.  Functionalization of single walled carbon nanotubes , 2006 .

[17]  Yann Garcia,et al.  Carboxylated, Fe-filled multiwalled carbon nanotubes as versatile catalysts for O2 reduction and H2 evolution reactions at physiological pH. , 2015, Chemistry.

[18]  Richard Martel,et al.  Controlling doping and carrier injection in carbon nanotube transistors , 2002 .

[19]  Bora Yoon,et al.  Surface-Anchored Poly(4-vinylpyridine)–Single-Walled Carbon Nanotube–Metal Composites for Gas Detection , 2016 .

[20]  Daniel P. Sanders,et al.  A General Model for Selectivity in Olefin Cross Metathesis. , 2004 .

[21]  R. Grubbs,et al.  The development of L2X2Ru=CHR olefin metathesis catalysts: an organometallic success story. , 2001, Accounts of chemical research.

[22]  J. Tour,et al.  Covalent chemistry of single-wall carbon nanotubes , 2002 .

[23]  John F. Fennell,et al.  Nanowire Chemical/Biological Sensors: Status and a Roadmap for the Future , 2016 .

[24]  Fei Wang,et al.  Diverse chemiresistors based upon covalently modified multiwalled carbon nanotubes. , 2011, Journal of the American Chemical Society.

[25]  S. Manesis,et al.  A Survey of Applications of Wireless Sensors and Wireless Sensor Networks , 2005, Proceedings of the 2005 IEEE International Symposium on, Mediterrean Conference on Control and Automation Intelligent Control, 2005..

[26]  T. Swager,et al.  Single-Walled Carbon Nanotube–Metalloporphyrin Chemiresistive Gas Sensor Arrays for Volatile Organic Compounds , 2015 .

[27]  V. C. Moore,et al.  Band Gap Fluorescence from Individual Single-Walled Carbon Nanotubes , 2002, Science.

[28]  Vikram Joshi,et al.  Nanoelectronic Carbon Dioxide Sensors , 2004 .

[29]  Shota Fujii,et al.  X‐ray absorption fine structure study on the role of solvent on polymerization of 3‐hexylthiophene with solid FeCl3 particles , 2015 .

[30]  J. Reynolds,et al.  Poly(3,4‐ethylenedioxythiophene) and Its Derivatives: Past, Present, and Future , 2000 .

[31]  Ming Zheng,et al.  DNA sequence motifs for structure-specific recognition and separation of carbon nanotubes , 2009, Nature.

[32]  M. Murray,et al.  Near-infrared absorptions of monomethylhydrazine , 1993 .

[33]  Richard D. McCullough,et al.  Employing MALDI-MS on Poly(alkylthiophenes): Analysis of Molecular Weights, Molecular Weight Distributions, End-Group Structures, and End-Group Modifications , 1999 .

[34]  Tsutomu Yokozawa,et al.  Chain-growth polymerization for poly(3-hexylthiophene) with a defined molecular weight and a low polydispersity , 2004 .

[35]  Arthur J. Epstein,et al.  Secondary doping in polyaniline , 1995 .

[36]  Ado Jorio,et al.  Raman Spectroscopy in Graphene Related Systems , 2011 .

[37]  Rodi Sferopoulos,et al.  A Review of Chemical Warfare Agent (CWA) Detector Technologies and Commercial-Off-The-Shelf Items , 2009 .

[38]  G. Sotzing,et al.  Electrochromic conducting polymers via electrochemical polymerization of bis(2-(3,4-ethylenedioxy)thienyl) monomers , 1996 .

[39]  Michael Sommer,et al.  Kumada Catalyst-Transfer Polycondensation: Mechanism, Opportunities, and Challenges. , 2011, Macromolecular rapid communications.

[40]  Riichiro Saito,et al.  Characterizing carbon nanotube samples with resonance Raman scattering , 2003 .

[41]  Davide Bonifazi,et al.  Magnetically Active Carbon Nanotubes at Work. , 2015, Chemistry.

[42]  Kong,et al.  Nanotube molecular wires as chemical sensors , 2000, Science.

[43]  T. Swager,et al.  Carbon nanotube/polythiophene chemiresistive sensors for chemical warfare agents. , 2008, Journal of the American Chemical Society.

[44]  Jin-Woo Han,et al.  Carbon Nanotube Based Humidity Sensor on Cellulose Paper , 2012 .

[45]  Young-Min Choi,et al.  Investigation of the humidity effect on the electrical properties of single-walled carbon nanotube transistors , 2005 .

[46]  Y. Weizmann,et al.  Sensory Arrays of Covalently Functionalized Single‐Walled Carbon Nanotubes for Explosive Detection , 2013 .

[47]  Joseph M. Azzarelli,et al.  Rapid prototyping of carbon-based chemiresistive gas sensors on paper , 2013, Proceedings of the National Academy of Sciences.

[48]  S. Bachilo,et al.  Analyzing absorption backgrounds in single-walled carbon nanotube spectra. , 2011, ACS nano.

[49]  R. D. Mccullough,et al.  Facile Synthesis of End-Functionalized Regioregular Poly(3-alkylthiophene)s via Modified Grignard Metathesis Reaction , 2005 .

[50]  John R. Reynolds,et al.  Poly[trans-bis(3,4-ethylenedioxythiophene)vinylene]: a low band-gap polymer with rapid redox switching capabilities between conducting transmissive and insulating absorptive states , 1995 .

[51]  T. Swager,et al.  Robust cyclohexanone selective chemiresistors based on single-walled carbon nanotubes. , 2013, Analytical chemistry.

[52]  Klaus Müllen,et al.  Why does matrix-assisted laser desorption/ionization time-of-flight mass spectrometry give incorrect results for broad polymer distributions? , 1996 .

[53]  Yi Lin,et al.  Functionalized carbon nanotubes: properties and applications. , 2002, Accounts of chemical research.

[54]  Jean-Luc Brédas,et al.  Electronic evolution of poly(3,4-ethylenedioxythiophene) (PEDOT): from the isolated chain to the pristine and heavily doped crystals. , 2008, Journal of the American Chemical Society.

[55]  Katherine A. Mirica,et al.  Employing Halogen Bonding Interactions in Chemiresistive Gas Sensors , 2016 .

[56]  R. Grubbs,et al.  Mechanism and activity of ruthenium olefin metathesis catalysts. , 2001, Journal of the American Chemical Society.

[57]  Timothy M Swager,et al.  Wireless gas detection with a smartphone via rf communication , 2014, Proceedings of the National Academy of Sciences.