Deprotonation-Induced Conductivity Shift of Polyethylenedioxythiophenes in Aqueous Solutions: The Effects of Side-Chain Length and Polymer Composition.

Deprotonation-induced conductivity shift of poly(3,4-ethylenedixoythiophene)s (PEDOTs) in aqueous solutions is a promising platform for chemical or biological sensor due to its large signal output and minimum effect from material morphology. Carboxylic acid group functionalized poly(Cn-EDOT-COOH)s are synthesized and electrodeposited on microelectrodes. The microelectrodes are utilized to study the effect of carboxylic acid side-chain length on the conductivity curve profiles in aqueous buffer with different pH. The conductivity shifts due to the buffer pH are effected by the length of the carboxylic acid side-chains. The shifts can be explained by the carboxylic acid dissociation property (pKa) at the solid-liquid interface, self-doping effect, and effective conjugation length. Conductivity profiles of poly(EDOT-OH-co-C₂-EDOT-COOH) copolymers are also studied. The shifts show linear relationship with the feed monomer composition used in electrochemical polymerization.