Reactivity of Ester Linkages and Pentaammineruthenium(III) at the Monolayer Assembly/Solution Interface
1996; American Chemical Society; Volume: 12; Issue: 25 Linguagem: Inglês
10.1021/la960027p
ISSN1520-5827
AutoresHal Van Ryswyk, Eric D. Turtle, Rachel A. Watson-Clark, T. A. Tanzer, Tobias Herman, Pek Y. Chong, Petra J. Waller, Aaron L. Taurog, Carl E. Wagner,
Tópico(s)Analytical Chemistry and Sensors
ResumoThe rate of base-mediated ester hydrolysis in monolayers of 11-mercaptoundecyl isonicotinate on gold is monitored by infrared spectroscopy and cyclic voltammetry. The hydrolysis product, a surface-confined alcohol, can be converted to a trifluoroacetate, increasing the sensitivity of infrared monitoring. Pentaammineruthenium(II) can be attached to the pendant isonicotinate either prior to or after monolayer assembly, leading to monolayers with a highly-charged monolayer/solution interface and a built-in electrochemical probe. The rate of ester hydrolysis within the monolayer is controlled by steric factors associated with monolayer packing and by the amount of charge at the monolayer/solution interface. The stability of the pendant Ru(III) complex is very sensitive to pH and interfacial charge. These results are correlated with Gouy−Chapman double-layer theory.
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