Synthesis and Characterization of Osmium Redox Polymer Mediators for Type II Biosensors

Monday, 14 October 2019: 15:20
Room 308 (The Hilton Atlanta)
M. C. Calhoun, C. Stachurski (Vanderbilt University), E. A. Gizzie (Northwestern University), A. W. Daniel, and D. E. Cliffel (Vanderbilt University)
Electrochemical sensors that utilize enzymes are a sensitive, inexpensive means of detecting biologically relevant analytes. These sensors are further categorized based on their construction and method of signal transport.1 Type I sensors consist of a crosslinked enzyme on an electrode surface, which are subject to interference from byproducts and other biological analytes. However, type II sensors alleviate this problem with the addition of a redox polymer layer, to assist in signal transportation, thus minimizing interference. There are a growing number of Type II sensors in the literature, however few are commercially available and typically suffer from poor structural and optical characterization.

Previously, an osmium-loaded poly(vinylimidazole) polymer (Os-PVI) was synthesized in order to avoid acetaminophen interference in enzyme sensor testing with successful results, yielding a type II sensor.2, 3 Given the success of the polymer, and the potential applications of the polymer for both enzyme and eletrogenerated-chemiluminescent sensors, it was important for Os-PVI to be properly characterized. Using previous literature, the two precursors Os(bpy)2Cl2 and poly(vinylimidazole) were synthesized. However, attempts at replication lead to the synthesis of an unknown osmium precursor. When coupled to PVI, a new osmium polymer was synthesized with new fluorescent and redox properties that did not match with the original Os-PVI polymer. All precursors and osmium polymers were characterized with 1H NMR, fluorescence, mass spectrometry, and cyclic voltammetry in order to provide a better understanding of these compounds and assist in the building of new sensors.

  1. Wang, J.; Ju, H.; Zhang, X., Electrochemical Sensors, Biosensors and Their Biomedical Applications. Academic Press: Amsterdam, 2008; Vol. 1st ed.
  2. Ohara, T. J.; Rajagopalan, R.; Heller, A., "Wired" Enzyme Electrodes for Amperometric Determination of Glucose or Lactate in the Presence of Interfering Substances. 1994, 66 (15), 2451-2457.
  3. Forster, R. J.; Vos, J. G., Synthesis, characterization, and properties of a series of osmium- and ruthenium-containing metallopolymers. Macromolecules 1990, 23 (20), 4372-4377.