Effect of Solution Composition on the Desorption Behavior of Self-Assembled Monolayers of Alkanethiols with Different Terminal Groups.

Voltammetry and chronoamperometry are used to study the effect of the solution composition on the desorption behavior of self-assembled monolayers of alkanethiols with approximately the same chain length but different terminal groups of thiols (R: –CH3, –CH2OH, and –NH2). The hydrophilic properties of the terminal groups for the studied thiols increased in the –CH3 –NH2 ≤ –CH2OH series. It is found that the anionic and cationic composition of electrolyte affected significantly the electrochemical stability and blocking ability of self-assembled monolayers of thiols with different terminal groups. It is established that the electrochemical stability and blocking ability of the self-assembled monolayers decreased in the Li⁺, Na⁺, K⁺ series in alkaline solutions regardless of the thiol terminal group. The cation nature in perchlorate and chloride solutions manifested itself only for thiol with the –NH2 terminal group. The shape of cathodic voltammograms changed for this thiol when passing from alkaline to and Сl^– medium, possibly owing to a change in the amino group protonation degree. [ABSTRACT FROM AUTHOR]

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