Stabilized potentiometric solid-state polyion sensors using silver-calixarene complexes as additives within ion-exchanger-based polymeric films

Abstract

Novel solid-state sensors for biomedically important polyions (i.e., heparin and protamine) that exhibit significantly enhanced initial EMF stability are prepared by incorporation of lipophilic silver-calixarene complexes along with the required ion-exchangers within polymeric films. A dithioether of tertiary butyl calix[4]arene together with its silver complex are added to the polyion sensing membranes which are deposited on a silver-epoxy conductor of a solid-state transducer. The silver-complex serves as a reversible electron transfer agent between the organic polymer film and the underlying solid-state conductor, resulting in highly reproducible starting EMF values and improved initial signal stability. This approach is further employed to devise a heparin sensing cartridge for blood measurements based on a novel differential measurement mode. One sensor responds to heparin, while the second identical solid-state sensor serves as a pseudo reference electrode with all heparin present in the sample within this half-cell complexed by the addition of excess protamine. The cartridges are evaluated by monitoring heparin response in spiked dog blood using poly(vinyl chloride) (PVC) blends and fluorinated silicone rubber (Dow Corning RTV 730) films containing appropriate levels of ion-exchanger and Ag + -calixarene/free calixarene additives.