Electrochemical investigation of Pb2+ binding and transport through a polymerized crystalline colloidal array...

The transport of Pb2+ through a sensory gel, a polymerized crystalline colloidal array hydrogel with immobilized benzo-18-crown-6, is important for understanding and optimizing the sensor. Square wave voltammetry at a Hg/Au electrode reveals many parameters. The partition coefficient for Pb2+ into a control gel (no crown ether), K(p), is 1.00 +/- 0.018 (errors reported are SEM). The porosity, epsilon, of the gel is 0.90 +/- 0.01. Log K(c) for complexation in the gel is 2.75 +/- 0.014. Log K(c) in aqueous solution for Pb2+ with the ligand 4-acryloylamidobenzo-18-crown-6 is 3.01 +/- 0.010 with dissociation rate k(d) = (8.34 +/- 0.45) x 10(2) s(-1) and association rate k(f) = (8.79 +/- 0.025) x 10(7) M(-1) s(-1). The partition coefficient of the ligand 4-acryloylamidobenzo-18-crown-6 into the control gel, K(p,L) is 2.07 +/- 0.15. The diffusion coefficient of Pb2+ in the control gel is 6.72 x 10(-6) +/- 0.12 cm(2)/s. For the sensor gel, but not control gel, diffusion coefficients are location dependent. The range of diffusion coefficients for Pb2+ in the probed locations was found to be (6.11-12.60) x 10(-7) cm(2)/s for 0.91 mM Pb2+ and (2.84-9.39) x 10(-7) cm(2)/s for 0.35 mM Pb2+. Lead binding in the sensor gel is slightly less avid than in solution. This is attributed, in part, to the demonstrated affinity of the ligand 4-acryloylamidobenzo-18-crown-6 to the gel. Diffusion coefficients determined for the sensor gel were found to be location dependent. This is attributed to heterogeneities in the crown concentration in the gel. Analysis of diffusion coefficients and rate constants show that diffusion and not chemical relaxation will limit the time response of the material.