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Accurate detection of L -Cysteine (Cyst) is critical because it is a recognized marker associated with diseases such as liver damage and kidney failure. Photoelectrochemical (PEC) sensor is an emerging strategy for biochemical analysis. However, the sensitivity of PEC sensor is limited by the high recombination rate of photogenerated electron-hole pairs. In this study, Au-mediated Z-scheme TiO 2 -Au-BiOI (HTNTs-Au-BOI) photoelectrochemical sensing platform for Cyst detection is proposed. Au NPs with plasmon resonance effect not only boost the light absorption but also facilitate the formation of Z-heterojunction HTNTs-Au-BOI through its own mediating effect. The Z-heterostructure with built-in electric field dramatically suppress the recombination of photogenerated electron-hole pairs and improve the sensitivity of the sensor. Meanwhile, the dual-specificity of Bi-S and Au-S bonds achieves a highly selective and sensitive detection of Cyst. The PEC sensor shows a wide linearity detection range of 80 nM-200 μM with a detection limit of 70 nM. The sensor also shows good results in the detection of serum samples, with a relative standard deviation (RSD) of 0.68–7.3 %. [Display omitted] • The Z-scheme TiO 2 -Au-BiOI is constructed using the mediation of Au NPs. • Au NPs with plasmonic resonance effect can significantly enhance the light absorption of TiO 2 -Au-BiOI. • Z-scheme HTNTs-Au-BiOI with built-in electric field suppress the recombination of photogenerated electron-hole pairs. • The dual-specificity of Bi-S and Au-S bonds achieve a highly selective and sensitive detection of Cyst. [ABSTRACT FROM AUTHOR]

Investigation of the mechanism of oxygen vacancy-regulated photoelectrochemical sensors for highly sensitive and selective determination of biomolecules containing electron-donating groups is an innovative research field. In this study, oxygen vacancy-regulated TiO 2 nanotube arrays (Ov-TNTs) with high photoelectrochemical activity were synthesized and applied to defect tetracycline hydrochloride (TC). The synergistic effect of oxygen vacancies and Ti3+ droves Ov-TNTs with a narrow energy band to generate more photogenerated carriers under irradiation. The photocurrent response of the oxygen vacancy-regulated photoelectrochemical sensor decreased with increasing TC concentration, which could be mainly attributed to adsorption of TC, which consumed part of the oxygen vacancies on the surface of Ov-TNTs. This system had excellent linearity in the range of 0.1–1000 nM with a detection limit of 0.33 nM (S/N = 3). In addition, the sensor was highly selective for TC determination due to the mutual electrostatic interaction between negatively charged TC-containing electron-donating groups (-NH 2 and -OH) and positively charged Ov-TNTs. This study provided a foundation for developing an oxygen vacancy-regulated adsorptive photoelectrochemical sensor. • The introduction of oxygen vacancies drives TNTs with narrow energy band to generate more photogenerated carriers. • Oxygen vacancies can be used as electron traps for preferential adsorption of TC molecules with electron-donating groups. • The photoelectrochemical sensor exhibits superior sensitivity and selectivity for TC detection. • The mechanism investigation shows that the adsorption of TC on the surface of Ov-TNTs decreases the oxygen vacancies and Ti3 + concentration, resulting in the gradual recovery of photocurrent to pure TNTs. [ABSTRACT FROM AUTHOR]

In this work, the typical honeycomb-nanoparticle heterostructure with honeycomb TiO 2 nanotube arrays (HTNTs) as light harvesting unit and Bi 2 MoO 6 nanoparticles (BMO) as recognition unit was prepared for highly sensitive and selective nano-enzymatic photoelectrochemical L-cysteine biosensor. [Display omitted] • The typical honeycomb-nanoparticle heterostructure between HTNTs and BMO improves the light harvesting behavior and the separation efficiency of the electron-hole pairs. • BMO nanoparticles fully dispersed on HTNTs with large specific surface area provides more sites for Cyst recognition. • Cyst can be specifically recognized through the Bi-S bonds. • The PEC enzyme-free biosensor shows good performance for Cyst with low detection limit and wide linear range. Improving light harvesting behavior and recognition sites of sensor is an effective way to achieve highly sensitive and selective detection of nano-enzymatic photoelectrochemical (PEC) L-cysteine (Cyst). In this work, the Bi 2 MoO 6 -TiO 2 composite (BMO-HTNTs) with honeycomb TiO 2 nanotube arrays (HTNTs) as light harvesting unit and Bi 2 MoO 6 nanoparticles (BMO) as recognition unit was prepared. The typical honeycomb-nanoparticle heterostructure between HTNTs and BMO improves the separation efficiency of the electron-hole pairs. Moreover, BMO nanoparticles fully dispersed on HTNTs with large specific surface area provide more sites for Cyst recognition. The composite exhibited the enhanced light absorption and higher photocurrent density at 0.2 V (vs. Ag/AgCl), which was 4 times than that of HTNTs under simulated light. Ingeniously, Cyst can not only be specifically recognized through the Bi-S bonds but also act as electron donor to scavenge the photogenerated holes of BMO-HTNTs, resulting in the increase of PEC responses. The PEC sensor showed superior analytical performance for Cyst detection with two linear regression equations in the range of 500 nM to 500 μM and a detection limit of 150 nM. The results of the enzyme-free sensor on practical urine and serum samples demonstrated its promising application in biological monitoring. [ABSTRACT FROM AUTHOR]