Ultrahigh peroxidase-like catalytic performance of Cu-N 4 and Cu-N 4 S active sites-containing reduced graphene oxide for sensitive electrochemical biosensing.

Autor: Le PG; Department of BioNano Technology, Gachon University, 1342 Seongnamdae-ro, Sujeong-gu, Seongnam, Gyeonggi, 13120, Republic of Korea; Department of Electronic Engineering, Gachon University, 1342 Seongnamdae-ro, Sujeong-gu, Seongnam, Gyeonggi, 13120, Republic of Korea., Le XA; Department of BioNano Technology, Gachon University, 1342 Seongnamdae-ro, Sujeong-gu, Seongnam, Gyeonggi, 13120, Republic of Korea., Duong HS; Department of BioNano Technology, Gachon University, 1342 Seongnamdae-ro, Sujeong-gu, Seongnam, Gyeonggi, 13120, Republic of Korea., Jung SH; Department of Materials Science and Engineering, Gachon University, 1342 Seongnamdae-ro, Sujeong-gu, Seongnam, Gyeonggi, 13120, Republic of Korea., Kim T; Department of Materials Science and Engineering, Gachon University, 1342 Seongnamdae-ro, Sujeong-gu, Seongnam, Gyeonggi, 13120, Republic of Korea., Kim MI; Department of BioNano Technology, Gachon University, 1342 Seongnamdae-ro, Sujeong-gu, Seongnam, Gyeonggi, 13120, Republic of Korea. Electronic address: moonil@gachon.ac.kr.
Jazyk: angličtina
Zdroj: Biosensors & bioelectronics [Biosens Bioelectron] 2024 Jul 01; Vol. 255, pp. 116259. Date of Electronic Publication: 2024 Mar 31.
DOI: 10.1016/j.bios.2024.116259
Abstrakt: Carbon-based nanozymes possessing peroxidase-like activity have attracted significant interest because of their potential to replace native peroxidases in biotechnology. Although various carbon-based nanozymes have been developed, their relatively low catalytic efficiency needs to be overcome to realize their practical utilization. Here, inspired by the elemental uniqueness of Cu and the doped elements N and S, as well as the active site structure of Cu-centered oxidoreductases, we developed a new carbon-based peroxidase-mimicking nanozyme, single-atom Cu-centered N- and S-codoped reduced graphene oxide (Cu-NS-rGO), which preserved many Cu-N 4 and Cu-N 4 S active sites and showed dramatically high peroxidase-like activity without any oxidase-like activity, yielding up to 2500-fold higher catalytic efficiency (k cat /K m ) than that of pristine rGO. The high catalytic activity of Cu-NS-rGO might be attributed to the acceleration of electron transfer from Cu single atom as well as synergistic effects from both Cu-N 4 and Cu-N 4 S active sites, which was theoretically confirmed by Gibbs free energy calculations using density functional theory. The prepared Cu-NS-rGO was then used to construct an electrochemical bioassay system for detecting choline and acetylcholine by coupling with the corresponding oxidases. Using this system, both target molecules were selectively determined with high sensitivity that was sufficient to clinically determine their levels in physiological fluids. Overall, this study will facilitate the development of nanocarbon-based nanozymes and their electrochemical biosensing applications, which can be extended to the development of miniaturized devices in point-of-care testing environments.
Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
(Copyright © 2024 Elsevier B.V. All rights reserved.)
Databáze: MEDLINE
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