Passive Sensor Materials based on Liquid Crystals

Research supported by this grant entitled “Passive Sensor Materials Based on Liquid Crystals” revolved around an investigation of liquid crystalline materials for use in passive sensors for chemical agents, including sulfur and phosphorus-containing compounds. The research was founded on the discovery in the Abbott research group at University of Wisconsin that competitive molecular interactions between metal ion receptors, liquid crystals and targeted analytes can lead to easily visualized and quantified changes in the orientations of films of liquid crystals. These changes in optical appearance of the liquid crystal offer the basis of a new approach for measurement and monitoring of exposure to specific and non-specific chemical environments. Selective detection of simulants of G agents and mustard gas in the part-per-billion concentration (in vapor) on time scales of tens of seconds was demonstrated. Tolerance to potentially interfering compounds (e.g., water) at concentrations 100,000 times higher than the targeted simulants was also shown. Research described in this report focused on the translation of these past findings into the design of nanostructured liquid crystalline materials that exhibited the sensitivity and specificity demonstrated in past studies with the added benefits of (i) mechanical robustness and (ii) processability such that a range of potential DoD applications are enabled. (a) Papers published in peer-reviewed journals (N/A for none) List of papers submitted or published that acknowledge ARO support during this reporting period. List the papers, including journal references, in the following categories: Katie D. Cadwell, Nathan A. Lockwood, Barbara A. Nellis, Mahriah E. Alf, Colin Willis, and Nicholas L. Abbott, “ Detection of organophosphorous nerve agents using liquid crystals supported on chemically functionalized surfaces”. Sensors and Actuators B, Chemical, 128, 91-98, 2007 Koenig, G. M., Jr.; Gettelfinger, B. T.; de Pablo, J. J.; Abbott, N. L. Using Localized Surface Plasmon Resonances to Probe the Nanoscopic Origins of Adsorbate-Driven Ordering Transitions of Liquid Crystals in Contact with Chemically Functionalized Gold Nanodots Nano Lett. 8(8); 2362-2368, 2008. Sri Sivakumar, Jugal K. Gupta, Nicholas L. Abbott, and Frank Caruso, “Monodisperse Emulsions through Templating Polyelectrolyte Multilayer Capsules”, Chemistry of Materials, 20(6), 2063-2065, 2008. S.S. Sridharamurthy, K. D. Cadwell, N. L. Abbott, and H. Jiang, “A microfabricated structure for detection of vapor-phase analytes based on orientational transitions of liquid crystals”, Smart Materials and Structures, 17, 1-4, 2008 Hung, F.R.; Gettelfinger, B.T.; Koenig, G.M.; Abbott, N.L.; de Pablo, J.J.,”Nanoparticles in Nematic Liquid Crystals: Interactions with Nanochannels”, Journal of Chemical Physics, 127, 124702-, 2007. Gary M. Koenig Jr., Maria-Victoria Meli, Joon-Seo Park, Juan J. de Pablo, and Nicholas L. Abbott “Coupling of the Plasmon Resonance of Chemically Functionalized Gold Nanoparticles to Local Order in Thermotropic Liquid Crystals”, Chemistry of Materials, 19 (5): 1053-1061, 2007. Gupta, JK; Sivakumar, S; Caruso, F, Abbott, NL, Size-Dependent Ordering of Liquid Crystals Observed in Polymeric Capsules with Micrometer and Smaller Diameter, Angewandte Chemie-International Edition, 48(9): 1652-1655,2009. Gupta, JK; Zimmerman, JS; de Pablo, JJ, Abbott NL , Characterization of Adsorbate-Induced Ordering Transitions of Liquid Crystals within Monodisperse Droplets, Langmuir, 25 (16),9016-9024, 2009. Agarwal, A; Huang, E; Palecek, S, Abbott NL Optically Responsive and Mechanically Tunable Colloid-In-Liquid Crystal Gels that Support Growth of Fibroblasts, Advanced Materials, 20 (24), 4804-+, 2008. Gupta, JK; Abbott, NL., Principles for Manipulation of the Lateral Organization of Aqueous-Soluble Surface-Active Molecules at the Liquid Crystal-Aqueous Interface, Langmuir, 25 (4), 2026-2033, 2009. Sivakumar, S; Wark, KL; Gupta, JK, Abbott, NL., Liquid Crystal Emulsions as the Basis of Biological Sensors for the Optical Detection of Bacteria and Viruses, Advanced Functional Materials, 19 (14), 2260-2265, 2009. Lin, I-H; Meli, M-V; Abbott, NL, Ordering transitions in micrometer-thick films of nematic liquid crystals driven by self-assembly of ganglioside GM1. J Colloid Interface Sci Volume: 336 (1), 90-99, 2009. Kinsinger, MI; Buck, ME; Campos, F, Abbott, NL, Dynamic Ordering Transitions of Liquid Crystals Driven by Interfacial Complexes Formed between Polyanions and Amphiphilic Polyamines, Langmuir, 24 (23), 13231-13236, 2008. Koenig, GM; Gettelfinger, BT; de Pablo, JJ, Abbott, NL Using localized surface plasmon resonances to probe the nanoscopic origins of adsorbate-driven ordering transitions of liquid crystals in contact with chemically functionalized gold nanodots, Nanoletters, 8(8), 2362-2368, 2008. Gupta, JK; Tjipto, E; Zelikin, AN, Abbott NL , Characterization of the growth of polyelectrolyte multilayers formed at interfaces between aqueous phases and thermotropic liquid crystals, Langmuir, 24(10): 5534-5542, 2008. Hunter, JT; Pal, SK; Abbott, NL Adsorbate-Induced Ordering Transitions of Nematic Liquid Crystals on Surfaces Decorated with Aluminum Perchlorate Salts, ACS Applied Materials and Interfaces, 2 (7), 1857-1865, 2010. Yiqun Bai, Xiaosong Liu, Peter Cook, Nicholas L. Abbott, F. J. Himpsel, “Characterization of Surfaces Presenting Covalently Immobilized Oligopeptides Using Near-Edge X-ray Absorption Fine Structure Spectroscopy”, Langmuir 26 (9), 6464-6470, 2010. Yang, ZQ; Gupta, JK; Kishimoto, K, Kato, T; Abbott, NL, Design of Biomolecular Interfaces Using Liquid Crystals Containing Oligomeric Ethylene Glycol Advanced Functional Materials, 20 (13), 2098-2106, 2010. Michael I. Kinsinger, Maren E. Buck, Nicholas L. Abbott, David M. Lynn “Immobilization of Polymer-Decorated Liquid Crystal Droplets on Chemically Tailored Surfaces”, Langmuir 26 (12), 10234-10242, 2010. Lowe AM, Ozer BH, Bai Y, Bertics PJ, Abbott NL. “Design of Surfaces for Liquid Crystal-based Bioanalytical Assays”. ACS Appl Mater Interfaces. 2(3):722-31, 2010. Gettelfinger, BT; Moreno-Razo, JA; Koenig,; Hernandez-Ortiz, JP; Abbott, NL; de Pablo, JJ “Flow induced deformation of defects around nanoparticles and nanodroplets suspended in liquid crystals” Soft Matter, 6 (5): 896-901 2010. Koenig, GM; Lin, IH; Abbott, NL “Chemoresponsive Assemblies of Microparticles at Liquid Crystalline Interfaces”, Proceedings of the National Academy of Sciences, 107 (9), 3998-4003, 2010. Kinsinger MI, Buck ME, Meli MV, Abbott, NL, Lynn DM, “Langmuir Films of Flexible Polymers Transferred to Aqueous/Liquid Crystal Interfaces Induce Uniform Azimuthal Alignment of the Liquid Crystal”, Journal of Colloid and Interface Science, 341 (1) 124-135, 2010 (b) Papers published in non-peer-reviewed journals or in conference proceedings (N/A for none) None 24.00 Number of Papers published in peer-reviewed journals: Number of Papers published in non peer-reviewed journals: ACS Colloids Symposium, NCSU, June 2008 MRS meeting in San Francisco, March, 2008 GRC on Chemistry at Interfaces, Waterville Valley, July, 2008 AIChE meeting in Salt Lake City, November, 2007. Abbott, N.L. “Amplification of Biomolecular Interactions using Liquid Crystals”, Keynote Lecture at Soft Matter Symposium, ACS Colloid and Surface Science Meeting, North Carolina State University, June 2008. Abbott, N.L..”Nanostructure of Complexes of DNA and Redox-Active Surfactants for Spatial and Temporal Control of Transfection”, International Conference on Bionanotechnology, Dublin, Ireland, July, 2008. Abbott, N.L., “Colloidal Interactions in Liquid Crystals”, Departmental Seminar, Chemical Engineering,,Virginia Tech, October, 2008. Abbott, N.L. “Biomolecular Analysis based on Liquid Crystals”, Innovative Molecular Analysis Program, National Cancer Institute, Cambridge, MA, October, 2008. Abbott, N.L., “Amplification of Biomolecular Interactions Based on Liquid Crystals”, Departmental Seminar, Chemical Engineering, Northwestern University, November, 2008. Abbott, N.L.”Optical Sensors for Biomolecules” Materials Research Society Meeting, December, 2008 Abbott, N.L. “Colloids Interactions in LC Systems”, ARO Workshop, Napa, CA, March, 2009. Abbott, N.L., ‘Amplication of Molecular Interactions using Liquid Crystals”, University of Pittburgh, PA, April 2009. 5th US-Sino Conference on Chemical Engineering, October 2009, Beijing "Colloidal and Interfacial Phenomena involving Liquid Crystals" ACS Meeting, DC, August 2009 "Directed Assembly of Colloids at Interfaces of Liquid Crystals" Columbia University, February, 2010, "Novel Colloidal and Interfacial Phenomena in Liquid Crystalline Systems" CBD Conference, November 2009, "Novel Materials based on Liquid Crystals that Respond to Targeted Chemical and Biological Environments" MIT, November 2009 "Novel Colloidal and Interfacial Phenomena in Liquid Crystalline Systems" ACS Meeting, San Francisco, March 2010 "Ordering Transitions at Aqueous-Liquid Crystal Interfaces Decorated with Functional Amphiphilic Polymers" ACS Meeting, San Francisco, March 2010 "Optically Responsive and Mechanically Tunable Colloid-in-Liquid Crystal Gels that Support Growth of Fibroblasts" Brandeis University, February 2010, "Novel Colloidal and Interfacial Phenomena in Liquid Crystalline Systems" (c) Presentations 0.00 Number of Presentations: 22.00 Non Peer-Reviewed Conference Proceeding publications (other than abstracts): Number of Non Peer-Reviewed Conference Proceeding publications (other than abstracts): 0 Peer-Reviewed Conference Proceeding publications (other than abstracts): (d) Manuscripts Number of Peer-Reviewed Conference Proceeding publications (other than abstracts): 0 Number of Manuscripts: 0.00 Patents Submitted Optically Responsive and Mechanically Tunable Colloid-in-Liquid Crystal Gels, filed with USPTO, 2008. Monodisperse Emulsions through Templating Polyelectrolyte Multilayer Capsules, filed with USPTO, 2008. Immobilization of Droplets of Liquid Crystals on Surfaces, filed with USPTO, 2009. Patents Awarded Awards 2011, Plenary Lecture, 11th European Conference on Liquid Crystals (Slovenia) 2011, Vilas Associate, University of Wisconsin-Madison