Adsorption of Enantiomeric Poly(lactide)s on Surface-Grafted Poly(l-lactide)

We show that resistance of densely grafted polymer layers to adsorption of chemically identical free chains, which is known to be caused by entropic expulsion of free chains from the grafted layer, can be suppressed using the grafted and free chains of opposite stereoconfiguration. Specifically, we study adsorption of poly(l-lactide) (PLLA) and its enantiomer poly(d-lactide) (PDLA) onto layers of surface-grafted PLLA in acetonitrile and chloroform by infrared spectroscopy (IR). The grafted layers with thicknesses ranging from 7 to 35 nm are produced by ring-opening polymerization of l-lactide from hydroxyl end-groups of a self-assembled monolayer on gold. The IR data indicate that adsorption on the bare gold surface is the same for the l- and d-form of the polymer. However, covering the gold with the surface-grafted PLLA produces a significant decline in the adsorption of free PLLA and, by contrast, a strong enhancement in the adsorption of free PDLA. In addition, the IR data indicate that the adsorbed PDLA chains are stereocomplexed with the grafted PLLA chains. Thus, entropic expulsion of free chains from the grafted layer, which is responsible for the resistance of surface-grafted PLLA to adsorption of free PLLA, is suppressed in the case of free PDLA by stereocomplexation between the grafted and free chains.