Abstract

• Defective Cu-doped In 2 S 3 (Cu: In 2 S 3 ) were successfully synthesized by using Cu 2+ as a dopant. • Cu doping can adjust the electronic structure and energy band structure of In 2 S 3 and produce the negative charged defects. • Cu: In 2 S 3 showed excellent PEC performance due to the enhanced visible light absorption and electron-hole separation. • A novel “signal-off” PEC sensor for VEGF 165 detection was constructed based on assembly and disassembly of nanocluster structure. • The sensor avoided difficult assembly of diverse signal quenchers, and exhibited excellent sensitivity and wide linear range. In this work, defective Cu-doped In 2 S 3 (Cu: In 2 S 3 ) was explored as photoactive material to fabricate a novel “signal-off” photoelectrochemical (PEC) sensing platform for ultrasensitive vascular endothelial growth factor 165 (VEGF 165 ) detection. The defective Cu: In 2 S 3 generated approximately ten times higher photocurrent than the pristine In 2 S 3 , which was attributed to the enhanced visible light absorption and electron-hole separation caused by the negative-charged defects induced by Cu doping. Moreover, an aptamer bridged nanocluster consisting of Cu: In 2 S 3 material and DNA strand was assembled on the electrode as an efficient PEC signal indicator. The immobilized photoactive Cu: In 2 S 3 could be released by recognition of the target VEGF 165 to achieve a “signal-off” biosensor. The proposed PEC sensor performs a desirable detection response in the range of 10 fM to 100 nM VEGF 165 with a low detection limit of 3 fM. This strategy not only avoided difficult assembly of diverse signal indicator and quenchers, but also significantly improved the detection sensitivity and linear range of PEC biosensor, offering a new perspective for construction of PEC biosensors for accurate, sensitive, and convenient bioanalysis and disease diagnosis.

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