Structural changes of the KcsA potassium channel fixed on gold electrode surface in the upright orientation were studied by surface-enhanced IR absorption spectroscopy (SEIRAS). Measurements were performed at neutral pH, where the activation gate is kept closed. Band intensities were enhanced for the asymmetric (1565 cm(-1)) and symmetric (1405 cm(-1)) OCO-carboxylate groups at negative electrode potentials in the K+ solution, but not in the Na+ solution. Even for the reverse-oriented channel, the enhanced OCO-carboxylate band was evident at negative potential. When TBA was loaded in the central cavity, the K+-specific OCO band was not elicited. These results indicate that the negative electrode potential renders the local K+ concentration accumulated at the vicinity of the electrode surface, and the KcsA channel bathed in high K+ changes conformation of the selectivity filter from the collapsed to the open, and OCO-carboxylate groups (D80 and E71) in the back of the filter were rearranged. Crown Copyright (C) 2013 Published by Elsevier B. V. All rights reserved.