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