Organic reactivity at interfaces has recently become the focus of considerable research attention because the importance to electronics, biosensors, and medical devices, however the role of pressure and time on accelerating surface reactions remains poorly understood because of the dearth of tools for studying these processes. We have shown recently that force can be used as a method for inducing a Diels-Alder reaction on graphene that would not otherwise occur,1 and herein we describe a quantitative model that accounts for the role of force, time, and monolayer chain length affect  the velocity of the surface reaction. Specifically, we use massively parallel elastomer tip arrays to control the force between alkynes on the tips and azide terminated monolayers on glass and gold substrates. Using both fluorescent and electrochemical methods, the rate constant and activation volume of the Huisgen reaction on the substrates were determined, revealing that the monolayer chain lengths are a critical factor that determine the reaction activation volume. The tool developed here is a powerful method for studying force induced organic reactions, which could lead to breakthroughs in molecular electronics, biosensing, and nanofabrication.(1)   Bian, S. D.; Scott, A. M.; Cao, Y.; Liang, Y.; Osuna, S.; Houk, K. N.; Braunschweig, A. B. J. Am. Chem. Soc. 2013 , 135, 9240.

Tip-based nanoreactor for studying force accelerated surface reactions

248th National Meeting (2014)

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