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

Peer reviewed: 
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Scholarly level: 
Faculty/Staff
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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

Date created: 
2017-03-22
Identifier: 
DOI: 10.1021/acs.jpcc.7b01135
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.

Language: 
English
Document type: 
Article
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Rights remain with the author.
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Sponsor(s): 
Natural Sciences and Engineering Research Council of Canada (NSERC)
Natural Science Foundation of China
China Scholarship Council
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