Direct electrochemistry of hemoglobin adsorbed on self-assembled monolayers with different head groups or chain length

The electrochemical behaviors of hemoglobin (Hb) were studied by adsorbing Hb on the gold electrodes modified with self-assembled monolayers (SAMs) of different terminal groups and alkyl chain length. Specifically, through adsorbing the Hb molecules onto the SAMs of 3-mercaptopropanoic acid (MPA), 1-propanethiol (PT) and cysteamine hydrochloride (cys), the influences of the terminal groups of alkanethiols on the electron transfer of Hb were examined. A quasi-reversible redox process was observed when Hb was adsorbed on the MPA-modified electrode. However, an irreversible reduction process and no redox response were shown when Hb molecules were adsorbed on the SAMs of PT and cys-modified electrodes, respectively. The dependence of the direct electrochemical response of Hb on the alkyl chain length of alkanethiols (n) was further investigated on the SAMs of HS(CH2)nCOOH (n = 1, 2, 5 and 10). When n was 1, Hb showed a weak current response. When n were 2 and 5, quasi-reversible redox processes with nearly similar electron transfer rate constants (ks) of 0.49 and 0.47 s−1 were obtained, respectively. Increasing the number of methylene groups within carboxyl alkanethiol to 10 resulted in a significant decrease of the electron transfer rate and current response of Hb. The observations indicated that the SAM of MPA can provide suitable properties to keep Hb in a favorable adsorption state for direct electron transfer (DET). Furthermore, the direct electrochemistry of the Hb adsorbed on the SAM of MPA was studied in detail.