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Construction of a self-calibrating ratiometric SERS platform based on nanoenzyme-mediated antagonistic Raman signal for determination of total antioxidant capacity

Wang, Xu ; Ding, Jiacheng ; Che, Yandong ; Pullerits, Tõnu LU orcid ; Li, Wenjie ; Yang, Yanqiu and Song, Peng (2027) In Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy 365.
Abstract

In response to the limitations of traditional total antioxidant capacity (TAC) determination methods—namely limited sensitivity and weak anti-interference ability—as well as the reliance on toxic hydrogen peroxide in conventional nanozyme-based sensing systems, silver nanoparticles (HA-AgNPs) with enzyme-mimicking catalytic activity were synthesized using hydroxylamine hydrochloride as the reducing agent. These HA-AgNPs were further integrated with the ABTS (2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid)) substrate to construct a dual-site ratiometric sensing platform based on surface-enhanced Raman scattering (SERS). Experimental results demonstrated that HA-AgNPs efficiently catalyzed the oxidation of ABTS using dissolved... (More)

In response to the limitations of traditional total antioxidant capacity (TAC) determination methods—namely limited sensitivity and weak anti-interference ability—as well as the reliance on toxic hydrogen peroxide in conventional nanozyme-based sensing systems, silver nanoparticles (HA-AgNPs) with enzyme-mimicking catalytic activity were synthesized using hydroxylamine hydrochloride as the reducing agent. These HA-AgNPs were further integrated with the ABTS (2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid)) substrate to construct a dual-site ratiometric sensing platform based on surface-enhanced Raman scattering (SERS). Experimental results demonstrated that HA-AgNPs efficiently catalyzed the oxidation of ABTS using dissolved oxygen from air, eliminating the requirement for externally supplied hydrogen peroxide. The resulting oxidized ABTS (oxABTS) generated a strong Raman signal at 1405 cm−1. In contrast, the antioxidant substances were capable of reducing oxABTS, resulting in a concurrent decrease in the 1405 cm−1 signal intensity and a synchronous enhancement of the 1601 cm−1 Raman band, resulting in mutually antagonistic Raman signals. Using this reverse correlation between the two characteristic peaks, a ratiometric quantitative detection method was established. The system exhibited a linear response toward ascorbic acid over a concentration range of 10−9 to 10−5 mol/L, with a limit of detection as low as 0.1 nmol/L. Overall, the developed hydrogen peroxide-free nanozyme-based SERS sensing system is simple to operate and highly sensitive, providing a promising approach for rapid screening of total antioxidant capacity in food samples.

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author
; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Enzyme-like oxidase activity, Opposing Raman signal, SERS, Total antioxidant capacity
in
Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
volume
365
article number
128693
pages
10 pages
publisher
Elsevier
external identifiers
  • scopus:105049169027
  • pmid:42700641
ISSN
1386-1425
DOI
10.1016/j.saa.2026.128693
language
English
LU publication?
yes
additional info
Publisher Copyright: © 2026 Elsevier B.V.
id
73db9699-00cb-4cac-890b-684ef508b2b4
date added to LUP
2026-09-29 15:29:39
date last changed
2026-10-12 09:30:15
@article{73db9699-00cb-4cac-890b-684ef508b2b4,
  abstract     = {{<p>In response to the limitations of traditional total antioxidant capacity (TAC) determination methods—namely limited sensitivity and weak anti-interference ability—as well as the reliance on toxic hydrogen peroxide in conventional nanozyme-based sensing systems, silver nanoparticles (HA-AgNPs) with enzyme-mimicking catalytic activity were synthesized using hydroxylamine hydrochloride as the reducing agent. These HA-AgNPs were further integrated with the ABTS (2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid)) substrate to construct a dual-site ratiometric sensing platform based on surface-enhanced Raman scattering (SERS). Experimental results demonstrated that HA-AgNPs efficiently catalyzed the oxidation of ABTS using dissolved oxygen from air, eliminating the requirement for externally supplied hydrogen peroxide. The resulting oxidized ABTS (oxABTS) generated a strong Raman signal at 1405 cm<sup>−1</sup>. In contrast, the antioxidant substances were capable of reducing oxABTS, resulting in a concurrent decrease in the 1405 cm<sup>−1</sup> signal intensity and a synchronous enhancement of the 1601 cm<sup>−1</sup> Raman band, resulting in mutually antagonistic Raman signals. Using this reverse correlation between the two characteristic peaks, a ratiometric quantitative detection method was established. The system exhibited a linear response toward ascorbic acid over a concentration range of 10<sup>−9</sup> to 10<sup>−5</sup> mol/L, with a limit of detection as low as 0.1 nmol/L. Overall, the developed hydrogen peroxide-free nanozyme-based SERS sensing system is simple to operate and highly sensitive, providing a promising approach for rapid screening of total antioxidant capacity in food samples.</p>}},
  author       = {{Wang, Xu and Ding, Jiacheng and Che, Yandong and Pullerits, Tõnu and Li, Wenjie and Yang, Yanqiu and Song, Peng}},
  issn         = {{1386-1425}},
  keywords     = {{Enzyme-like oxidase activity; Opposing Raman signal; SERS; Total antioxidant capacity}},
  language     = {{eng}},
  month        = {{01}},
  publisher    = {{Elsevier}},
  series       = {{Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy}},
  title        = {{Construction of a self-calibrating ratiometric SERS platform based on nanoenzyme-mediated antagonistic Raman signal for determination of total antioxidant capacity}},
  url          = {{http://dx.doi.org/10.1016/j.saa.2026.128693}},
  doi          = {{10.1016/j.saa.2026.128693}},
  volume       = {{365}},
  year         = {{2027}},
}