title: Load-induced transitions in the lubricity of adsorbed poly(L-lysine)-g-dextran as a function of polysaccharide chain density.
abstract: Chain-density gradients of poly(l-lysine)-graft-dextran (PLL-g-dex), a synthetic comblike copolymer with a poly(l-lysine) backbone grafted with dextran side chains, were fabricated on an oxidized silicon substrate. The influence of the changing dextran chain density along the gradient on the local coefficient of friction was investigated via colloidal-probe lateral force microscopy. Both in composition and structure, PLL-g-dex shares many similarities with bottlebrush biomolecules present in natural lubricating systems, while having the advantage of being well-characterized in terms of both architecture and adsorption behavior on negatively charged oxide surfaces. The results indicate that the transition of the dextran chain density from the mushroom into the brush regime coincides with a sharp reduction in friction at low loads. Above a critical load, the friction increases by more than an order of magnitude, likely signaling a pressure-induced change in the brush conformation at the contact area and a corresponding change in the mechanism of sliding. The onset of this higher-friction regime is moved to higher loads as the chain density of the film is increased. While in the low-load (and low-friction) regime, increased chain density leads to lower friction, in the high-load (high-friction) regime, increased chain density was found to lead to higher friction.
authors: Laboratory for Surface Science and Technology, Department of Materials, ETH Zurich, Wolfgang-Pauli-Strasse 10, CH-8093 Zurich, Switzerland.
authors: Kenneth J
authors: KJ
authors: Rosenberg
authors: Tolga
authors: T
authors: Goren
authors: Rowena
authors: R
authors: Crockett
authors: Nicholas D
authors: ND
authors: Spencer
mesh_terms: D000327:Adsorption; D003911:Dextrans / Q000737:chemistry*; D008153:Lubrication; D018625:Microscopy, Atomic Force; D011107:Polylysine / Q000031:analogs & derivatives* / Q000737:chemistry; D011134:Polysaccharides / Q000737:chemistry*; D012822:Silicon Dioxide / Q000737:chemistry
chemical_list: D003911:Dextrans; D011134:Polysaccharides; C113090:poly(lysine)-graft-dextran; D011107:Polylysine; D012822:Silicon Dioxide