Understanding
the relation between the chemical bonding and the
electron-transfer (ET) reaction of surface-confined hemin (a five-coordinated
Fe-porphyrin-with-chlorine complex) is a special interest in the biomimicking
studies of heme proteins. Owing to the difficulty in ET function,
scanty electrochemical reports of hemin in aqueous solution were reported.
It has been noticed that in most of the reported procedures, the sixth
axial coordination position of the hemin complex has been unknowingly
turned by attaching with water molecules (potential cycling in alkaline
conditions or heating), solvents such as ethanol and dimethyl sulfoxide,
and nitrogen-donating compounds that have helped for the heme ET reaction.
In this work, a systematic effort has been taken to find out the contribution
of hemin and its axial bond coordination with π–π
interaction, hydrogen bonding, and hydrophobic binding systems toward
the ET reaction. Various graphitic carbons such as graphitized mesoporous
carbon (GMC), mesoporous carbon-hydrophilic and hydrophobic units,
graphite nanopowder, graphene oxide, single-walled carbon, multiwalled
carbon nanotube (MWCNT), and carboxylic acid-functionalized MWCNT
(as a source for π–π interaction, hydrogen bonding,
and hydrophobic environment) along with the amino functional group
of chitosan (Chit; as an axial site coordinating system) have been
tested by modifying them as a hemin hybrid on a glassy carbon electrode
(GCE). In addition, a gold nanoparticle (Aunano) system
was combined with the above matrix as a molecular wiring agent, and
its role was examined. A highly stable and well-defined redox peak
at an apparent formal potential (Eo′) of −320 mV versus Ag/AgCl with the highest surface excess
of 120 × 10–10 mol cm–2 was
noticed with the GCE/Aunano–GMC@hemin–Chit
hybrid system, wherein all interactive features have been utilized.
Omitting any of the individual interactions resulted in either decreased
(with Aunano) or nil current response. As applications,
efficient bio-electrocatalytic reduction and sensing of dissolved
oxygen and hydrogen peroxide have been demonstrated.