Pearson's principle-inspired hollow metal sulfide for amplified photoelectrochemical immunoassay for disease-related protein

Bin Li; Libin Guo; Lilin Ge; Hang Fai Kwok

doi:10.1016/j.bios.2022.114210

Pearson's principle-inspired hollow metal sulfide for amplified photoelectrochemical immunoassay for disease-related protein

Biosens Bioelectron. 2023 Feb 1:221:114210. doi: 10.1016/j.bios.2022.114210. Epub 2022 Mar 21.

Authors

Bin Li¹, Libin Guo², Lilin Ge³, Hang Fai Kwok⁴

Affiliations

¹ Collaborative Innovation Center of Chinese Medicinal Resources Industrialization, Nanjing University of Chinese Medicine, Nanjing, 210023, China; Institute of Translational Medicine, Faculty of Health Sciences, University of Macau, Avenida de Universidade, Taipa, Macau.
² Department of Biomedical Sciences, Faculty of Health Sciences, University of Macau, Avenida de Universidade, Taipa, Macau; Institute of Translational Medicine, Faculty of Health Sciences, University of Macau, Avenida de Universidade, Taipa, Macau.
³ Collaborative Innovation Center of Chinese Medicinal Resources Industrialization, Nanjing University of Chinese Medicine, Nanjing, 210023, China. Electronic address: gelilin@njucm.edu.cn.
⁴ Department of Biomedical Sciences, Faculty of Health Sciences, University of Macau, Avenida de Universidade, Taipa, Macau; Institute of Translational Medicine, Faculty of Health Sciences, University of Macau, Avenida de Universidade, Taipa, Macau; MoE Frontiers Science Center for Precision Oncology, University of Macau, Avenida de Universidade, Taipa, Macau. Electronic address: hfkwok@um.edu.mo.

PMID: 35718654
DOI: 10.1016/j.bios.2022.114210

Abstract

Designing a universal route for rational synthesis of a family of hollow multinary chalcogenide semiconductors for photoelectrochemical biosensors is still facing to the enormous challenges ahead. Herein a template-assisted Cu₂O surface vulcanization and etching through a Pearson's hard and soft acid-base (HSAB) principle was utilized to synthesize hollow Cu_2-xS photoactive materials for photocurrent detection of prostate-specific antigen (PSA). We initially synthesized cubic Cu₂O and further surface sulfidation and HCl etching to obtain cubic Cu_2-xS. Inspiringly, stirring of CuS, phosphine (TBP: tributylphosphine) and other metal salts could replace Cu⁺ ions to obtain new metal sulfides without changing the framework, size and thickness of the original material. This interesting phenomenon could be explained by HSAB theory, which soft base was favorable for combining soft acid (Cu⁺) to drive Cu⁺ out of the framework. Based on the results, HSAB-based reaction system was applied to develop novel photoelectrochemical PSA immunoassay. Polymetallic-doped sulfides (Zn_xCd_1-xS) had better photocurrent response than pure binary sulfides. A copper oxide (CuO)-labeled detection antibody is captured in a microplate along with a sandwich immunoassay in the presence of target PSA. Subsequently, the CuO nanoparticles were dissociated by hydrochloric acid, releasing a large amount of copper ions to participate in the cation exchange reaction with Zn_xCd_1-xS. Such excellent photoelectric conversion materials could sensitively detect target PSA with a wide linear range from 1.0 pg/mL to 10 ng/mL at a limit of detection down to 0.32 pg/mL. Additionally, favorable stability, great anti-interference ability, easy-fabrication, low-cost, and satisfactory accuracy for the analysis of actual samples were acquired. Importantly, the concept of cation exchange reaction can be widely used to synthesize advanced nanomaterials for fabrication of high-efficiency biosensing systems.

Keywords: Hard and soft acid-base principle; Pearson's principle; Photoelectrochemical immunoassay; Prostate-specific antigen.

MeSH terms

Biosensing Techniques* / methods
Cadmium
Copper
Electrochemical Techniques / methods
Humans
Immunoassay / methods
Limit of Detection
Male
Metal Nanoparticles*
Prostate-Specific Antigen / analysis
Sulfides

Substances

Prostate-Specific Antigen
hydroxysuccinimidyl-4-azidobenzoate
Cadmium
Copper
Sulfides