Atomic force microscopy with chemically functionalized colloidal probes was used to study "acidbase" interactions between poly(vinyl alcohol) (PVA) and a metal surface. By using well-defined model surfaces, we have studied the adhesion forces between a hydroxylated surface and cantilever tips with varying hydroxyl content. Decreasing the amount of available hydroxyl groups dramatically reduced the observed adhesion force. The calculated bond energy for each cantilever tip was found to be in the range of typical hydrogen bond energies, i.e., 10-40 kJ/mol, suggesting that the acid-base interactions are pre-dominately hydrogen bonding. Similarly, the force versus distance curves using PVA functionalized colloidal probes showed a strong dependence on the chemical functionality of the tip and the degree of acetylation of the intervening PVA. It was observed that, with an increase in the acetyl content of the PVA, the adhesion force decreased. (c) 2006 Wiley Periodicals, Inc.