Modulating the Redox Property of a Flavin Analog Through Adjustment of Its Microenvironment in a Self-Assembled Monolayer

Abstract
Self-assembled monolayers (SAMs) have been used to examine the effects of electrostatic interactions and changing microenvironment on the pH-dependent redox properties of a flavin analog. The pKa value of the N1 proton for the reduced flavin analog was determined to be ~9.7 in the SAM of disulfide 5, 8.5 in the SAM of disulfide 7, and 6.7 when free in solution. The pyridinium ion of 7 stabilizes the anionic form of reduced flavin analog and provides a dielectric medium more closely resembling that experienced by the flavin analog free in solution.

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