Chemical sensors based on receptor-doped polymeric membranes were developed for over 60 analytes. They are routinely used worldwide in clinical chemistry for well over a billion measurements per year. Unfortunately, their lifetimes are limited by lipids and hydrophobic proteins that adsorb onto or are extracted into these membranes. This hinders their wider use, in particular for the long-term implantation into the human body. Perfluorocarbon matrixes have great promise to solve this problem of sensor lifetime because their low polarity limits the solubility of lipids and proteins. The extraordinarily low polarity of perfluorocarbons is illustrated by the following example: On the pi * scale of solvent polarity, water has a pi* value of 1, hexane defines 0, and perfluorooctane has the astounding value of-0.41. Indeed, it is well documented that lipids are poorly soluble in perfluorocarbons. Therefore, it is expected that nonpolar perfluorinated membrane matrixes will not lose their selectivies when exposed to biological fluids containing lipids and hydrophobic proteins. Moreover, nonpolar perfluorinated matrixes (i) will exhibit much higher selectivities than conventional receptor-doped sensor matrixes because lipophilic interferents are hardly solvated in perfluorinated phases, (ii) are chemically very inert, and (iii) were shown to promote cell growth on their surface to a much lesser extent than most polymers presently used for receptor-based sensors. Despite the attractiveness of perfluorinated phases, the current literature does not describe any receptorbased sensor with a nonpolar perfluorinated matrix. Neither receptors nor electrolyte salts that are soluble in perfluorocarbon phases were reported. This research will develop perfluorinated polymeric matrixes and fluorophilic ion exchanger sites required for the preparation of receptor-based sensors. Three representative fluorophilic receptors will be synthesized and used for the preparation of potentiometric sensors. The robustness of these sensors will be tested with pure solutions of individual lipids, blood serum and urine samples. In brief, specific goals include the development of (i) fluorophilic cations and anions suitable as ionic sites for potentiometric sensors, (ii) a fluorophilic electrolyte salt, (iii) perfluorinated polymers suitable as matrixes for potentiometric sensors, (iv) proton-, creatininium-, and chloride-selective sensors based on perfluorinated membranes for applications in biological samples, and (v) perfluorinated sensing membranes surface-modified with poly(ethylene glycol) for a further improvement of their biocompatibility. The introduction of perfluorinated sensor matrixes will enhance the selectivity, robustness and lifetime of chemical sensors for clinical chemistry. It will also permit other novel uses of receptor-based chemical sensors under harsh conditions, such as long-term environmental monitoring with sensor networks for the prediction of earthquakes and process control in the food industry and manufacturing.

Agency
National Institute of Health (NIH)
Institute
National Institute of Biomedical Imaging and Bioengineering (NIBIB)
Type
Research Project (R01)
Project #
1R01EB005225-01
Application #
6904356
Study Section
Special Emphasis Panel (ZRG1-BECM (01))
Program Officer
Korte, Brenda
Project Start
2005-06-01
Project End
2008-05-31
Budget Start
2005-06-01
Budget End
2006-05-31
Support Year
1
Fiscal Year
2005
Total Cost
$218,732
Indirect Cost
Name
University of Minnesota Twin Cities
Department
Chemistry
Type
Schools of Arts and Sciences
DUNS #
555917996
City
Minneapolis
State
MN
Country
United States
Zip Code
55455
Anderson, Evan L; Gingery, Nicole M; Boswell, Paul G et al. (2016) Ion Aggregation and R3N+-C(R)-H···NR3 Hydrogen Bonding in a Fluorous Phase. J Phys Chem B 120:11239-11246
Miyake, Masafumi; Chen, Li D; Pozzi, Gianluca et al. (2012) Ion-selective electrodes with unusual response functions: simultaneous formation of ionophore-primary ion complexes with different stoichiometries. Anal Chem 84:1104-11
Chen, Li D; Mandal, Debaprasad; Pozzi, Gianluca et al. (2011) Potentiometric sensors based on fluorous membranes doped with highly selective ionophores for carbonate. J Am Chem Soc 133:20869-77
Lai, Chun-Ze; Fierke, Melissa A; Corrêa da Costa, Rosenildo et al. (2010) Highly selective detection of silver in the low ppt range with ion-selective electrodes based on ionophore-doped fluorous membranes. Anal Chem 82:7634-40
Fierke, Melissa A; Lai, Chun-Ze; Buhlmann, Philippe et al. (2010) Effects of architecture and surface chemistry of three-dimensionally ordered macroporous carbon solid contacts on performance of ion-selective electrodes. Anal Chem 82:680-8
Olson, Eric J; Boswell, Paul G; Givot, Bradley L et al. (2010) Electrochemistry in Media of Exceptionally Low Polarity: Voltammetry with a Fluorous Solvent. J Electroanal Chem (Lausanne) 639:154-160
Lai, Chun-Ze; Reardon, Molly E; Boswell, Paul G et al. (2010) Cation-Coordinating Properties of Perfluoro-15-Crown-5. J Fluor Chem 131:42-46
Lai, Chun-Ze; Koseoglu, Secil S; Lugert, Elizabeth C et al. (2009) Fluorous polymeric membranes for ionophore-based ion-selective potentiometry: how inert is Teflon AF? J Am Chem Soc 131:1598-1606
Lai, Chun-Ze; Joyer, Marti M; Fierke, Melissa A et al. (2009) Subnanomolar Detection Limit Application of Ion-Selective Electrodes with Three-Dimensionally Ordered Macroporous (3DOM) Carbon Solid Contacts. J Solid State Electrochem 13:123-128
Boswell, Paul G; Szijjarto, Csongor; Jurisch, Markus et al. (2008) Fluorophilic ionophores for potentiometric pH determinations with fluorous membranes of exceptional selectivity. Anal Chem 80:2084-90

Showing the most recent 10 out of 12 publications