Monolithic Peptide–Nucleic Acid Hybrid Functioning as an Artificial Microperoxidase Koji Nakano Junichi Tanabe Ryoich Ishimatsu Toshihiko Imato 10.1021/acs.bioconjchem.7b00216.s001 https://acs.figshare.com/articles/journal_contribution/Monolithic_Peptide_Nucleic_Acid_Hybrid_Functioning_as_an_Artificial_Microperoxidase/5244661 A new peptide nucleic acid (PNA) with an installed peroxidase function has been developed. Fmoc solid phase peptide synthesis prepared a PNA hybrid (VQKCAQCHTVE-(C<sub>2</sub>H<sub>4</sub>O)<sub>2</sub>CH<sub>2</sub>-[PNA­(T)]<sub>6</sub>-G) that renders the microperoxidase backbone, followed by reconstitution with hemin. The resulting holocompound catalyzed the oxidation of 3,3′,5,5′-tetramthylbenzidine by H<sub>2</sub>O<sub>2</sub> to 50% that of natural microperoxidase-11, whereas the apo-form and hemin gave no responses. The peroxidase domain was found to be active toward direct electrochemistry and the PNA hybrid served for gene sensor; in the presence of the target DNA (5′-CAT­GTA­TAAA­AAA-3′), an electrode-attached DNA probe (5′-TsTs­TsTs­TsTC­TCAT­ACA­TG-3′) showed the ferric-to-ferrous quasi-reversible wave (−276 mV vs Ag/AgCl) through sandwich hybridization. Moreover, the hybridization product could accept H<sub>2</sub>O<sub>2</sub> as an oxidant to enhance the reduction current, which occurred likely based on the iron­(II)-center-recycling with specific rate constant of 0.19 s<sup>–1</sup>. 2017-07-11 00:00:00 peroxidase function Hybrid Functioning hybridization product phase peptide synthesis hemin CH sandwich hybridization peroxidase domain H 2 O 2 microperoxidase backbone DNA gene sensor VQKCAQCHTVE Artificial Microperoxidase PNA