title: Brownian dynamics simulation of peeling a strongly-adsorbed polymer molecule from a frictionless substrate.
abstract: We used brownian dynamics to study the peeling of a polymer molecule, represented by a freely jointed chain, from a frictionless surface in an implicit solvent with parameters representative of single-stranded DNA adsorbed on graphite. For slow peeling rates, simulations match the predictions of an equilibrium statistical thermodynamic model. We show that deviations from equilibrium peeling forces are dominated by a combination of Stokes (viscous) drag forces acting on the desorbed section of the chain and a finite rate of hopping over a desorption barrier. Characteristic velocities separating equilibrium and nonequilibrium regimes are many orders of magnitude higher than values accessible in force spectroscopy experiments. Finite probe stiffness resulted in disappearance of force spikes due to desorption of individual links predicted by the statistical thermodynamic model under displacement control. Probe fluctuations also masked sharp transitions in peeling force between blocks of distinct sequences, indicating limitation in the ability of single-molecule force spectroscopy to distinguish small differences in homologous molecular structures.
authors.affiliation: Department of Chemical Engineering, Lehigh University, Bethlehem, Pennsylvania, Pennsylvania 18015, United States.
authors.forename: Sara
authors.initials: S
authors.lastname: Iliafar
authors.forename: Dmitri
authors.initials: D
authors.lastname: Vezenov
authors.forename: Anand
authors.initials: A
authors.lastname: Jagota
mesh_terms: D000327:Adsorption; D004277:DNA, Single-Stranded / Q000737:chemistry*; D006108:Graphite / Q000737:chemistry*; D008956:Models, Chemical; D056004:Molecular Dynamics Simulation; D010316:Particle Size; D011108:Polymers / Q000737:chemistry*; D013499:Surface Properties; D013816:Thermodynamics
chemical_list: D004277:DNA, Single-Stranded; D011108:Polymers; D006108:Graphite