Anal. Chem. 2000, 72, 3449-3454.

Preparation and Characterization of Thermoresponsive Poly(N-isopropylacrylamide-co-acrylic acid) Hydrogels: Studies with Electroactive Probes

Steven C. Petrovic, Weimin Zhang, and Malgorzata Ciszkowska*

Department of Chemistry, Brooklyn College, The City University of New York, Brooklyn, New York 11210-2889


A new method of preparing thermoresponsive hydrogels consisting of N-isopropylacrylamide (NIPA) and acrylic acid (AA), with a well-defined concentration of an electroactive probe, 1,1'-ferrocenedimethanol (Fc(MeOH)2), is described, and a comparison of the physical and electrochemical properties of NIPA-AA gels with those of aqueous solutions is presented. The NIPA-AA gels undergo a discontinuous volume phase transition at 45 degC; this transition results in a release of approximately 40% of the solution mass from the gel phase. Characterization of hydrogels with electroactive probes is performed using electroanalytical techniques and FTIR and UV/vis spectroscopies. Steady-state voltammetry and chronoamperometry at platinum disk microelectrodes are used to measure the diffusion coefficient of Fc(MeOH)2 in gels under a wide range of experimental conditions. Similar diffusion coefficients for Fc(MeOH)2 in NIPA-AA gels are obtained by either electroanalytical technique at temperatures lower than 20 degC. The uncertainty in the Fc(MeOH)2 concentration in the gels, resulting from the discontinuous volume change transition, necessitated the use of concentration-independent chronoamperometric data (i.e. the chronoamperometric response divided by the steady-state current obtained at sufficiently long times) to obtain reliable diffusion coefficient values for Fc(MeOH)2. For temperatures above the volume phase transition, changes of concentration of Fc(MeOH)2 are detected in a copolymeric collapsed phase.