The techniques of molecular imprinting and sensitized lanthanide luminescence have been combined to create the basis for a sensor that can selectively measure a specific organophosphorous compound. A complex of polymerizable sensitizing ligand europium (III) and an organophosphorous compound are copolymerized in a cross-linked polymer matrix. The best coordinators are trifluoromethyl substituted b-diketones. The best polymerization mechanism is by Reversible Addition Fragmentation Transfer polymerization. This approach is allowing the production of soluble processable imprinted materials. Analogous methodologies are currently being applied to the production of sensors for the detection and determination of drugs of abuse, explosives and meat spoilage. Drugs are measured in an analogous manner to the nerve agents while the explosives are being detected by the production of charge-transfer complexes between the explosives molecules, (acceptor) and immobilized amines (donor). Meat spoilage sensing is obtained using luminescence from a transition metal macrocyclic complex.
An additional thrust is to develop new solid phase extractants for the removal of metal ions from environmental and waste water and to serve as the basis for selective ion sensors. Rather than continuing to test existing extractants by an Edisonian approach in the hope that an excellent extractant may be found, we rely on chemical insights into what makes a good extractant. The sources of these insights include coordination number, coordination geometry, ionic size, ionic shape, and thermodynamic affinity. Selectivity is obtained by providing the polymeric extractants with cavities lined with complexing ligands so arranged as to match the charge, coordination number, coordination geometry, and size of the metal ion. These cavity-containing polymers are produced by using the metal ion as a template around which polymerizable monomeric complexing ligands are polymerized. The complexing ligands are ones containing functional groups known to form highly stable complexes with a specific metal ion and less stable complexes with other cations. We have developed sequestering agents for lead and uranium as well as electrochemical and optical sensors based on this approach.
Southard, G. E. and Murray, G. M., “Molecularly Imprinted Polymer Receptors for Sensors and Arrays,” in Principles of Bacterial Detection: Biosensors, Recognition Receptors and Microsystems, Zourob, M., Elwary, S. and Turner, A. Eds., Springer Verlag, 2010.
Southard, G. E., Van Houten, K. A., Hofstra, A. A. and Murray, G. M, "Synthetic and Spectroscopic Characterization of Molecularly Imprinted Polymer Phosphonate Sensors," in Polymers and Materials for Anti-Terrorism and Homeland Defense, ACS Symposium Series , Reynolds, J G. and Lawson, G. E., Eds., American Chemical Society, Washington, D. C., 2008.
Southard, G. E., Van Houten, K. A and Murray, G. M, "Soluble and Processable Phosphonate Sensing Star Molecularly Imprinted Polymers," Macromolecules, 40 (5) 1395-1400 (2007).
Southard, G. E., Ott Jr., E. W. Van Houten, K. A and Murray, G. M, "Luminescent Sensing of Organophosphates Using Imprinted Polymers Prepared by RAFT Polymerization," Analytica Chimica Acta, 581 (2) 202-207 (2007).
Southard, G. E., Van Houten, K. A. and Murray, G. M., "Heck Cross-Coupling for Synthesizing Metal Complexing Monomers," Synthesis, 2006 (15) 2475-2477 (2006).
Southard, G. E. and Murray, G. M., "Synthesis of Vinyl Substituted Beta-Diketones for Polymerizable Metal Complexes," Journal of Organic Chemistry, 70 (22) 9036-9039 (2005).
Bell, L. M. and Murray, G. M., "Selective Photo-reduction of N-nitrosamines Combined with Micellar Electrokinetic Chromatography and Laser Fluorimetric Detection," Journal of Chromatography, B., 826, 160-168 (2005).
Owens, G. S., Southard, G. E., Van Houten, K. A. and Murray, G. M., "Molecularly Imprinted Ion Exchange Resin for Fe3+, Separation Science and Technology, 40, 2205-2211 (2005).
Kimaro, A, Kelly, L. A. and Murray, G. M., "Synthesis and Characterization of Molecularly Imprinted Uranyl Ion Exchange Resins," Separation Science and Technology, 40, 2035-2052 (2005).
Murray, G. M. and Southard G. E., “Metal Ion Selective Molecularly Imprinted Materials,” in Molecular Imprinting: Science and Technology, Yan, M. and Ramstrom, O., Eds., Marcel Dekker, 2005.
Murray, G. M. and Southard, G. E., “Optical Transduction Schemes for Imprinted Polymer Sensors,” in Molecularly Imprinted Materials, Kofinas, P., Roberts, M. J., Sellergren, B. Eds., Materials Research Society Symposium Series Volume 787, Warrendale, PA, 2004.
Boyd, J. W., Cobb, G. P., Southard, G. E. and Murray, G. M. “Development of Molecularly Imprinted Polymer Sensors for Chemical Warfare Agents,” JHUAPL Technical Digest, 25, 44-49 (2004).
Murray, G. M. and Southard, G. E., "Synthetic and Spectroscopic Characterization of Molecularly Imprinted Polymer Phosphonate Sensors," Polymer Preprints, 45(1) 535-536 (2004).
Perry, A. S. and Murray, G. M., "In-line Fiber Optic Light Filter," Applied Spectroscopy, 57, 722-723 (2003).
Murray, G. M. and Southard, G. E., “Molecularly Imprinted Ionomers,” in Molecularly Imprinted Materials-Sensors and Other Devices, Shea, K. J., Yan, M., Roberts, M. J., Eds., Materials Research Society Symposium Series Volume 723, Warrendale, PA, 2002.
Murray, G. M. and Southard, G. E., "Sensors for Chemical Weapons Detection," IEEE Instrumentation and Measurement Magazine, 5(4) 12-21 (2002).
Murray G. M. and Southard, G. E. "Molecularly Imprinted Ionomers, M3.3" MRS Proceedings Volume 723, 2002.
Kimaro, A., Kelly, L. A. and Murray G. M., Molecularly Imprinted Ionically Permeable Membrane for Uranyl Ion, Chemical Communications, 1282-1283 (2001).
Murray, G. M. and Uy, O. M. " Ionic Sensors Based on Molecularly Imprinted Polymers," in Molecularly Imprinted Polymers, Sellergren, B., Ed., Elsevier, Amsterdam, 2001.
Murray, G. M., et al., “Method and Apparatus for Detection of Bio-aerosols,” Patent # 7,830,515, November 9, 2010.
Charles, H. K. and Murray, G. M., "Authentication of Products Using Molecularly Imprinted Polymers," Patent # 7,799,568, September 21, 2010.
Southard, G. E. and Murray, G.M., “Processable Molecularly Imprinted Polymers,” Patent # 7678870, March 16, 2010.
Murray, G. M., et al., “Method and Apparatus for Detection of Bio-aerosols,” U. S. Patent # 7,494,769, February 24, 2009.
Murray, G. M., Uy, O. M. and Jenkins, A. L., “Polymer Based Lanthanide Luminescent Sensors for the Detection of Organophosphorus Compounds,” U.S. Patent # 7,416,703, August 26, 2008.
Murray, G. M., “Polymer Based Permeable Membrane for Removal of Ions” U.S. Patent #. 7,279,096, October 9, 2007.
Murray, G. M., Ko, H. W. and Southard, G. E., "Neutron Detection Based on Boron Activated Liquid Scintillation, U.S. Patent # 7,126,148, October 24, 2006.
Perry, A. S. and Murray, G. M., Fiber Optic Coupler with In Line Component, U.S. Patent # 7,118,287, October 10, 2006.
Southard, G. E. and Murray, G. M., "Process for Preparing Vinyl Substituted Beta-diketones," U.S. Patent # 7,067,702, June 27, 2006.
Murray, G. M., Cain; R. P., Carkhuff; B. G., Weiskopf; F., "Techniques for Sensing Chloride Ions in Wet or Dry Media," U.S. Patent # 7,063,781, June 20, 2006.
Schwartz, P. D., Murray, G. M., Uy, O. M., Le, B. Q., Stott, D. D., Lew, A. L., Ling, S. X., and Suter, J. J., "Apparatus and Methods for Detecting Explosives and Other Substances," U.S. Patent #. 6,967,103, November 22, 2005.
Kelly, C. A., Murray, G. M., and Uy, O. M., “Method of Making a Polymeric Food Spoilage Sensor,” U.S. Patent #6,924,147, August 2, 2005, 2005.
Murray, G. M., Arnold, B. A., and Lawrence, D. S., "Molecularly Imprinted Polymer Sensor for Explosives," U. S. Patent # 6,872,786, March 29, 2005.
Murray, G. M., Kelly, C. A., Uy, O. M. Hunter, L. H. and Lawrence, D. S., "Method of Inhibiting Methamphetamine Synthesis," U.S. Patent # 6,852,891, February 8, 2005.
Murray, G. M., "Polymer Based Permeable Membrane for Removal of Ions," U.S. Patent #6,780,323, August 24, 2004.
Murray, G. M., "Molecularly Imprinted Polymer Solution Anion Sensor," U.S. Patent #6,749,811, June 15, 2004.
Kelly, C. A., Murray, G. M., and Uy, O. M., “Polymeric Food Spoilage Sensor,” U.S. Patent #6,593,142, July 15, 2003.
Murray, G. M., "Site Selective Ion Exchange Resins Templated for Lead (II) Ion and Methods and Devices for Their Use," U. S. Patent # 5,814,671, September 29, 1998.