Adsorption of polyacrylic acid on self-assembled monolayers investigated by single-molecule force spectroscopy

Abstract

Single-molecule force spectroscopy was used to study the adsorption and desorption processes of individual polyacrylic acid (PAA) chains from self-assembled monolayers (SAMs) with different terminal groups (CH3, OH, COOH). PAA was grafted to the tip of an AFM cantilever and all measurements were recorded with the same tip. For the OH- and the COOH-SAM, the desorption force was found to be independent of the salt concentration for NaCl, as well as for CaSO4. On CH3-SAM, a repulsive electrostatic interaction was found with NaCl in solution whereas a slightly attractive electrostatic interaction occurred with CaSO4 in solution. On the OH- and the COOH-terminated SAM, the non-electrostatic contributions to the desorption forces are of comparable magnitude (∼50–65 pN) whereas the non-electrostatic contribution for the CH3-terminated SAM is significantly higher (∼80–90 pN). Additional experimental findings concerning the length, the total number of adsorption events and the number of multiple polymer strands adsorbed in parallel, support the assumption that this difference in adsorption force is due to a different quality of the solvent for the polyacrylic acid chains at the SAM–water interface. Comparative surface pressure measurements at the air–water interface revealed a surface energy for polyacrylic acid of 30 mJ m2 which would correspond to a force contribution of ∼10 pN to the desorption force. This is in good agreement with the experimental results on hydrophobic SAMs. For further characterization of the surfaces the pH was varied from 3 to 11 at constant salt concentration (for a NaCl concentration of 100 mM and a CaSO4 concentration of 5 mM, respectively). In the presence of NaCl, the desorption force was found to be independent of the pH for all three substrates. For CaSO4, the desorption force was pH-independent for the OH- and the CH3-SAM. In the case of the COOH-SAM, a jump from 60 to 90 pN was recorded at pH 8, which we attribute to the formation of salt bridges between the polyacrylic acid chain and the COOH-SAM at higher pH.