AbstractGlassy carbon electrodes (GCE) modified by a bilayer of phospholipids (BLM) have been used to monitor the passage of redox probes and ferrocene‐labelled peptides across lipid membranes of an anionic (DOPG) or a zwitterionic (globally neutral DPhPC) phospholipid. The gel‐phase neutral DPhPC showed a strong association with neutral probes like ferrocene methanol but expelled positively or negatively charged species, as observed on cyclic voltammograms. Anionic DOPG underwent a strong electrostatic interaction with the positively charged hexaamine ruthenium(III) complex, leading to aggregates that caused swelling and destructuration of the BLM. With positively charged ferrocene‐tagged peptides, DOPG‐modified GCE allowed the observation of cyclic voltammograms exhibiting both a potential shift with respect to bare GCE and increased peak intensity, accounting for the slow but favored partition of the peptides between the BLM and the solution.
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