Host–Guest Interaction at Molecular Interfaces: Binding of Cucurbit[7]uril on Ferrocenyl Self-Assembled Monolayers on Gold
Author(s) -
Qi Lin,
Huihui Tian,
Huibo Shao,
HuaZhong Yu
Publication year - 2017
Publication title -
the journal of physical chemistry c
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.401
H-Index - 289
eISSN - 1932-7455
pISSN - 1932-7447
DOI - 10.1021/acs.jpcc.7b01135
Subject(s) - monolayer , supramolecular chemistry , chemistry , redox , ferrocene , dissociation constant , molecular recognition , binding constant , self assembled monolayer , molecular binding , cucurbituril , biomolecule , dissociation (chemistry) , crystallography , molecule , stereochemistry , binding site , inorganic chemistry , electrochemistry , organic chemistry , receptor , biochemistry , electrode
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
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