Revisiting the Response Mechanism of Polymeric Membrane Based Heparin Electrodes.

Potentiometric membrane electrodes that respond to heparin and other polyanions were introduced in the early 1990s. Herein, the mechanism of polymer membrane electrode type heparin sensors is revisited. The extraction/diffusion of heparin is studied via both potentiometric and impedance spectroscopic techniques using a pre-fractionated heparin preparation that contains polyanionic species > 10000 Daltons. The reversal in EMF response using this heparin preparation indicates diffusion of higher MW heparin fragments to the backside of the membrane. Diffusion coefficients are calculated using a novel formula derived from the phase boundary potential model and Fick's second law of diffusion. Impedance spectroscopy is also employed to show that high MW heparin species are extracted and diffuse across the PVC membranes.

Determination of solute descriptors by chromatographic methods.

The solvation parameter model is now well established as a useful tool for obtaining quantitative structure-property relationships for chemical, biomedical and environmental processes. The model correlates a free-energy related property of a system to six free-energy derived descriptors describing molecular properties. These molecular descriptors are defined as L (gas-liquid partition coefficient on hexadecane at 298K), V (McGowan's characteristic volume), E (excess molar refraction), S (dipolarity/polarizability), A (hydrogen-bond acidity), and B (hydrogen-bond basicity). McGowan's characteristic volume is trivially calculated from structure and the excess molar refraction can be calculated for liquids from their refractive index and easily estimated for solids. The remaining four descriptors are derived by experiment using (largely) two-phase partitioning, chromatography, and solubility measurements. In this article, the use of gas chromatography, reversed-phase liquid chromatography, micellar electrokinetic chromatography, and two-phase partitioning for determining solute descriptors is described. A large database of experimental retention factors and partition coefficients is constructed after first applying selection tools to remove unreliable experimental values and an optimized collection of varied compounds with descriptor values suitable for calibrating chromatographic systems is presented. These optimized descriptors are demonstrated to be robust and more suitable than other groups of descriptors characterizing the separation properties of chromatographic systems.