In-situ cation-exchange deposited Ag2S/In4SnS8 of Z-type heterojunction coupled with DNA recycling amplification for photoelectrochemical biosensing

Abstract

Herein, a novel photoelectrochemical (PEC) biosensor was developed utilizing an in situ cation-exchange method to deposit a high-performance Ag₂S/In₄SnS_8, a Z-type heterojunction with co-shared S atoms, as a signal indicator and using DNA recycling amplification for the sensitive and accurate detection of miRNA-141. The photosensitive Ag₂S deposited on the In₄SnS₈ surface not only facilitated the rapid generation of photoelectrons but also formed a Z-type heterojunction with In₄SnS₈, effectively inhibiting electron-hole pair recombination. This resulted in a considerable improvement in the photoelectric conversion efficiency of Ag₂S/In₄SnS_8, yielding an ∼ 120-fold increase in photocurrent compared to that of In₄SnS₈ under 660-nm visible-light irradiation. Furthermore, the arborescent DNA structure formed by hybrid chain reaction (HCR) enhanced the steric effect, thereby reducing the PEC response. Importantly, numerous quenchers MnPP competed for light absorption and captured photogenerated electrons in the valence bands of In₄SnS₈ and Ag₂S, reducing electron transfer to the electrode and further considerably reducing the photocurrent. This enabled the sensitive detection of miRNA-141 across a concentration range from 10 amol·L⁻¹ to 100 pmol·L⁻¹, with a limit of detection as low as 3.3 amol·L⁻¹ (S/N = 3). The proposed biosensor exhibits excellent stability and is expected to be applied for detecting clinically relevant disease markers.