Electrochemical investigation of the chloride effect on hemoglobin

Direct electron transfer between hemoglobin and gold electrode is achieved at both a bare and a 4, 4′-bipyridine-modified gold electrode in the presence of chloride ions. The addition of chloride to hemoglobin solution also increases the reversibility of the direct electrochemistry and shifts the formal potential of hemoglobin to the negative direction. While the existence of chloride does not significantly change the tertiary structure of the protein, it might induce a slight variation of the structure, which is beneficial to the electrochemical response. It is suggested that the chloride binding to hemoglobin is a combination of specific and unspecific bindings.