Functionalizing a Polyelectrolyte Complex with Chitosan Derivatives to Tailor Membrane Surface Properties

Polyelectrolyte complex (PEC) materials show promise in the development of tunable membranes for aqueous and organic solvent separations, as well as in the creation of surface layers for fouling control. In this study, we developed a polyelectrolyte complex (PEC) functionalized by negatively charged carboxymethyl chitosan (CMC-) and positively charged quaternized chitosan (QC+) to tailor its surface properties and antibacterial efficacy. CMC- and QC+ were prepared and characterized using FT-IR and ¹H NMR, which confirmed the presence of the carboxymethyl group and trimethylammonium group in CMC- and QC+ with 65.6% and 83.9% substitution, respectively. The CMC- functionalized PEC (CMC-/PEC) and QC+ functionalized PEC materials (QC+/PEC) were evaluated for their stability in water, resistance to organic and inorganic adsorption, and antibacterial action against a model microorganism, Pseudomonas putida. The results showed no release of chitosan derivatives after adsorption, and CMC-/PEC and QC+/PEC exhibited charge-based, selective repulsion of model organic and inorganic substances. Moreover, the functionalized PEC surfaces displayed lower bacterial attachment due to their smoother surfaces as compared to the bare ceramic membrane and their antimicrobial properties. Among the PEC samples, CMC-/PEC had the lowest cell attachment, while QC+/PEC showed the highest attachment due to electrostatic attraction. The ceramic and bare PEC surfaces were negligibly bactericidal, while cell viability decreased to 34.4 ± 10.2% and 30.6 ± 8.2% with the CMC-/PEC and QC+/PEC surfaces, respectively. In the filtration experiments, the unmodified PEC and CMC-/PEC showed lower rates of flux decline due to organic fouling than did the bare ceramic or QC+/PEC due to electrostatic repulsion. Furthermore, PECs as protective layers promoted much higher flux recoveries than simply backwashing the uncoated membranes. This surface tunability, then, enhances the potential of PECs either as fouling resistant materials or as a method to create a sacrificial, protective layer on surfaces that once fouled can be dissolved and re-established.