Reduction of Surface Hydrophobicity Using a Stimulus-Responsive Polysaccharide

The adsorption of carboxymethyl cellulose (CMC) onto a hydrophobic self-assembled monolayer has been characterized using the quartz crystal microbalance (with dissipation monitoring, QCM-D). Adsorption was studied as a function of initial solution conditions. CMC adsorbs to a greater extent at high ionic strength (10(-1) M KCl as opposed to 10(-2) M KCl) or low pH (3 as opposed to 9). The solution conditions that yielded the lowest initial adsorbed amount (10(-2) M KCl, pH 9) were used as a reference to investigate the response of the adsorbed layer to a switch in solution conditions after adsorption (i.e., to higher ionic strength (10(-1) M KCl) or lower pH (pH 3)). The adsorbed layer released significant amounts of hydration water after each solution switch, as determined by the QCM-D measurements. This expulsion of hydration water was fully reversible. For the two solution switches, reducing the solution pH resulted in a more pronounced change in the amount of hydration water within the adsorbed CMC, accompanied by a distinct conformational change, as determined from a QCM D-f plot. In addition to studying adsorption using QCM-D, the effect of adsorbed CMC on surface hydrophobicity has been investigated using captive bubble contact angle measurements. The effect of the polymer on the contact angle of the surface was seen to be greatest when adsorbed at low pH or at higher ionic strength. CMC was also seen to have a significantly enhanced ability to reduce the surface hydrophobicity after both the ionic strength and pH switches, lowering the advancing water contact angle by 6 and 23 degrees and the receding water contact angle by 10 and 40 degrees for the ionic strength and pH switches, respectively. As with the change in hydration water content, the change in the contact angle of the polymer-coated surface following the solution switches was reversible.