Enhanced electron transfer between gold nanoparticles and horseradish peroxidase reconstituted onto alkanethiol-modified hemin

•Horseradish peroxidase (r1HRP) was reconstituted onto C11-alkanethiol-conjugated hemin.•R1HRP was self-assembled on Au nanoparticle (NP) electrodes via the exposed thiol tail.•Electron transfer between r1HRP and electrode is enhanced when proceeding via the Au NP relay.•Demonstrated NP-biohybrid system allows advanced programmable design of bioelectronics interfaces.

Robust molecular bioelectronic devices require a programmable and efficient electronic communication between biological molecules and electrodes. With proteins it is often compromised by their uncontrollable assembly on electrodes that does not provide neither uniform nor efficient electron flow between proteins and electrodes. Here, horseradish peroxidase reconstituted onto C11-alkanethiol-conjugated hemin and self-assembled onto the gold nanoparticle (NP)-modified electrodes via the exposed alkanethiol tail exhibits enhanced electron transfer (ET), proceeding via the gold NP relay with the ET rate constant approaching 115 s− 1 vs. 14 s− 1 shown on bare gold, by this offering an advanced controllable design of interfaces for bioelectronic devices based on heme-containing enzymes with a non-covalently bound heme.

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