Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Dependence of an Interfacial Diels-Alder Reaction Kinetics on the Density of the Immobilized Dienophile: An Example of Phase-Separation

  • Min, Kyoung-Mi (Department of Biomedical Engineering, Dongguk University-Seoul) ;
  • Jung, Deok-Ho (Department of Biomedical Engineering, Dongguk University-Seoul) ;
  • Chae, Su-In (Department of Biomedical Engineering, Dongguk University-Seoul) ;
  • Kwon, Young-Eun (Department of Biomedical Engineering, Dongguk University-Seoul)
  • Received : 2011.02.25
  • Accepted : 2011.03.30
  • Published : 2011.05.20
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Abstract

Interfacial reactions kinetics often differ from kinetics of bulk reactions. Here, we describe how the density change of an immobilized reactant influences the kinetics of interfacial reactions. Self-assembled monolayers (SAMs) of alkanethiolates on gold were used as a model interface and the Diels-Alder reaction between immobilized quinones and soluble cyclopentadiene was used as a model reaction. The kinetic behavior was studied using varying concentrations of quinones. An unusual threshold density of quinones (${\Gamma}_c$ = 5.2-7.2%), at which the pseudo-first order rate constant started to vary as the reaction progressed, was observed. This unexpected kinetic behavior was attributed to the phase-separation phenomena of multi-component SAMs. Additional experiments using more phase-separated two-component SAMs supported this explanation by revealing a significant decrease in ${\Gamma}_c$ values. When the background hydroxyl group was replaced with carboxylic or phosphoric acid groups, ${\Gamma}_c$ was observed at below 1%. Also, more phase-separated thermodynamically controlled SAMs produced a lower critical density (3% < ${\Gamma}_c$ < 4.9%) than that of the less phaseseparated kinetically controlled SAMs (6.5% < ${\Gamma}_c$ < 8.9%).

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References

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