TY - JOUR
T1 - Monolayer packing, dehydration, and ink-binding dynamics at the molecular
AU - Gannon, Greg
AU - Larsson, J. Andreas
AU - Thompson, Damien
PY - 2009/4/30
Y1 - 2009/4/30
N2 - Gold-bound self-assembled monolayers (SAMs) terminating in β-cyclodextrin (β-CD) cavities provide a highly ordered surface array of hydrophobic binding pockets and so are used as "molecular printboards" for nanopatterning applications. The present work complements ongoing nanoscale experiments by providing the atom-scale structure, dynamics, and energetics of the printboard, which may aid the design of functional platforms for nanotechnology. We use fully atomistic molecular dynamics (MD) computer simulations to probe the printboard lattice constant, height, steric packing, hydrophobicity, and ink-binding properties as a function of gold-β-CD "linker" molecule and degree of binding to gold. The simulations reveal the stabilization associated with the experimentally observed surface lattice constant of ∼2 nm, alkanethioether linkers, and partial unbinding from gold. Additional ink-binding simulations indicate that multivalent ink molecules can offset disordering in the more loosely packed alkanethiol-linked printboard, with the attendant steric penalty similar in magnitude to the favorable multivalent ink:β-CD complexation.
AB - Gold-bound self-assembled monolayers (SAMs) terminating in β-cyclodextrin (β-CD) cavities provide a highly ordered surface array of hydrophobic binding pockets and so are used as "molecular printboards" for nanopatterning applications. The present work complements ongoing nanoscale experiments by providing the atom-scale structure, dynamics, and energetics of the printboard, which may aid the design of functional platforms for nanotechnology. We use fully atomistic molecular dynamics (MD) computer simulations to probe the printboard lattice constant, height, steric packing, hydrophobicity, and ink-binding properties as a function of gold-β-CD "linker" molecule and degree of binding to gold. The simulations reveal the stabilization associated with the experimentally observed surface lattice constant of ∼2 nm, alkanethioether linkers, and partial unbinding from gold. Additional ink-binding simulations indicate that multivalent ink molecules can offset disordering in the more loosely packed alkanethiol-linked printboard, with the attendant steric penalty similar in magnitude to the favorable multivalent ink:β-CD complexation.
UR - http://www.scopus.com/inward/record.url?scp=67049145195&partnerID=8YFLogxK
U2 - 10.1021/jp811189b
DO - 10.1021/jp811189b
M3 - Article
AN - SCOPUS:67049145195
SN - 1932-7447
VL - 113
SP - 7298
EP - 7304
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 17
ER -