title: A Thermodynamics Model for the Emergence of a Stripe-like Binary SAM on a Nanoparticle Surface.
abstract: It has been under debate if a self-assembled monolayer (SAM) with two immiscible ligands of different chain lengths and/or bulkiness can form a stripe-like pattern on a nanoparticle (NP) surface. The entropic gain upon such pattern formation due to difference in chain lengths and/or bulkiness has been proposed as the driving force in literature. Using atomistic discrete molecular dynamics simulations it is shown that stripe-like pattern could indeed emerge, but only for a subset of binary SAM systems. In addition to entropic contributions, the formation of a striped pattern also strongly depends upon interligand interactions governed by the physicochemical properties of the ligand constituents. Due to the interplay between entropy and enthalpy, a binary SAM system can be categorized into three different types depending on whether and under what condition a striped pattern can emerge. The results help clarify the ongoing debate and our proposed principle can aid in the engineering of novel binary SAMs on a NP surface.
authors.affiliation: Department of Physics and Astronomy, Clemson University, Clemson, SC, 29634, USA.
authors.forename: Xinwei
authors.initials: X
authors.lastname: Ge
authors.affiliation: ARC Centre of Excellence in Convergent, Bio-Nano Science and Technology, Monash Institute of Pharmaceutical Sciences, Monash University, Parkville, VIC, 3052, Australia.
authors.forename: Pu Chun
authors.initials: PC
authors.lastname: Ke
authors.affiliation: ARC Centre of Excellence in Convergent, Bio-Nano Science and Technology, Monash Institute of Pharmaceutical Sciences, Monash University, Parkville, VIC, 3052, Australia.|Department of Chemistry, Warwick University, Coventry, CV4 7AL, UK.
authors.forename: Thomas P
authors.initials: TP
authors.lastname: Davis
authors.affiliation: Department of Physics and Astronomy, Clemson University, Clemson, SC, 29634, USA.
authors.forename: Feng
authors.initials: F
authors.lastname: Ding
mesh_terms: D008956:Models, Chemical; D056004:Molecular Dynamics Simulation; D053758:Nanoparticles / Q000737:chemistry*; D013816:Thermodynamics
keywords: molecular dynamics; nanotechnology; self-assembled monolayers; self-assembly; striped nanoparticles