Host-guest Interaction at Molecular Interfaces: Binding of Cucurbit[7]uril on Ferrocenyl Self-assembled Monolayers on Gold

Resource type
Date created
2017-03-22
Authors/Contributors
Author: Qi, Lin
Author: Tian, Huihui
Author: Shao, Huibo
Abstract
Ferrocene (Fc) encapsulated cucurbit[7]uril (CB[7]) supramolecular host-guest complex (Fc@CB[7]) as a synthetic recognition pair has been widely adapted for coupling biomolecules and nanomaterials due to its ultra-high binding affinity. In this paper, we have explored the binding of CB[7] on binary ferrocenylundecanethiolate/octanethiolate self-assembled monolayer on gold (FcC11S-/C8S-Au), a model system to deepen our understanding of host-guest chemistry at molecular interfaces. It has been shown that upon incubation with CB[7] solution, the redox behavior FcC11S-/C8S-Au changes remarkably, i.e., a new pair of peaks appeared at more positive potential with narrowed widths. The ease of quantitation of surface bound-redox species (Fc+/Fc and Fc+@CB[7]/ Fc@CB[7]) enabled us to determine the thermodynamic formation constant of Fc@CB[7] at FcC11S-/C8S-Au (7.3±1.8 × 104 M-1). With time-dependent redox responses, we were able to, for the first time, deduce both the binding and dissociation rate constants, 2.8±0.3 × 103 M-1s-1 and 0.08±0.01 s-1, respectively. These results showed substantial differences both thermodynamically and kinetically for the formation of host-guest inclusion complex at molecular interfaces with respect to solution-diffused, homogenous environments.
Document
Identifier
DOI: 10.1021/acs.jpcc.7b01135
Published as
Qi, L.; Tian, H.; Shao, H.; Yu, H.-Z. Host-guest Interaction at Molecular Interfaces: Binding of Cucurbit[7]uril on Ferrocenyl Self-assembled Monolayers on Gold. Journal of Physical Chemistry C, 2017, 121 (14), pp 7985–7992.DOI: 10.1021/acs.jpcc.7b01135
Publication title
Journal of Physical Chemistry C
Document title
Host-guest Interaction at Molecular Interfaces: Binding of Cucurbit[7]uril on Ferrocenyl Self-assembled Monolayers on Gold
Date
2017
Volume
121
Issue
14
First page
7985
Last page
7992
Publisher DOI
10.1021/acs.jpcc.7b01135
Copyright statement
Copyright is held by the author(s).
Scholarly level
Peer reviewed?
Yes
Language
Member of collection