Phase transitions of an ionic liquid self-assembled monolayer on Au |
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Authors: | Branca Mathieu Correia-Ledo Debby Bolduc Olivier R Ratel Mathieu Schmitzer Andreea R Masson Jean-Francois |
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Institution: | Département de Chimie, Université de Montréal, C. P. 6128 Succ. Centre-Ville, Montréal, Qc, Canada H3C 3J7. |
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Abstract: | The properties of a surface modified with an ionic liquid self-assembled monolayer (IL-SAM) can be tuned by simply changing the deposition temperature. Mid-IR, SERS, and molecular modelling demonstrated that 1-(12-mercaptododecyl)-3-methylimidazolium bromide (MDMIBr) exhibited a crystalline monolayer for deposition temperatures below 25 °C. Above 25 °C, the aliphatic chain collapsed into a disordered conformation. At 40 °C, another phase transition occurs due to the imidazolium group tilting parallel to the surface. Consequently, the wettability of IL-SAM was tuned over a broad range of contact angle (from 20° to nearly 40°) by varying the deposition temperature. Permeation of redox mediators to a Au electrode coated with MDMIBr strongly depends on the net charge of the redox mediator. Electron transfer was excellent for neutral and negatively charged redox mediators on electrodes coated with IL-SAM regardless of deposition temperature. |
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