基于Zr-MOFs光电化学传感用于同型半胱氨酸的检测

以4-羧基苯基卟啉（TCPP）作为配体,金属锆（Zr）作为配位金属,通过水热法合成Zr-MOFs。以Zr-MOFs材料作为光电活性材料构建了阴极光电化学传感器用于检测同型半胱氨酸（Hcy）。当λ > 420 nm的氙灯光源照射Zr-MOFs时,处于价带（VB）上的电子（e^-）跃迁至导带（CB）,并在价带上产生空穴（h⁺）,从而产生光电流。同型半胱氨酸的加入会阻碍电子的传递,从而造成阴极光电流降低。当目标物浓度为10 ~ 100 nmol·L^-1和100 ~ 1000 nmol·L^-1时,光电流信号变化值与目标物浓度呈线性关系,且检出限为2.17 nmol·L^-1,制备的传感器具有良好的稳定性和选择性。

Photoelectrochemical Sensing Based on Zr-MOFs for Homocysteine Detection

Due to the independent form of the light source and detection system, photoelectrochemical (PEC) sensor has the advantages of low background, high sensitivity and simple operation. So far, PEC systems have been widely used in the fields including the actual detection of metal ions, biological antibodies or antigens in environmental pollutants. When the photosensitive material is irradiated by a light source with an energy being equal to or greater than its band gap, electrons (e^-) transition occurs from the valence band to the conduction band, leaving a hole (h⁺), at the same time, the generated electron-hole pair (e^-/h⁺) separate, and migrate to the electrode surface and electrolyte to generate photocurrent or photovoltage. When the target analyte is added, it will interact with its recognition molecule, and affect the separation or migration process of the charge, thereby, causing a change in the photocurrent. Metal organic framework (MOF) is a material composed of metal ions and organic linking groups. They have adjustable porosity, functional surface and massive conjugate back bone. These unique characteristics of MOF have been extensively explored in various fields. Zr-MOFs were synthesized use 4-carboxyphenylporphyrin (TCPP) as the ligand, and metal zirconium (Zr) as the coordination metal. Using Zr-MOFs as the photoelectrically active material, a cathode photoelectrochemical sensor was constructed to detect homocysteine (Hcy). A three-electrode system, consisting of Zr-MOFs/FTO electrode, Pt electrode and Ag/AgCl electrode, was inserted into 0.01 mol·L^-1 HEPES solution to prepare the sensor. An aqueous solution of homocysteine was added to the electrolyte, allowing it to stand for 5 min. Cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the reaction process and the electron transfer process between optoelectronic materials. When the Xe lamp with λ > 420 nm is used to irradiate Zr-MOFs, electrons (e ^-) in the valence band transfer to the conduction band, and holes (h⁺) are generated in the valence band, thereby, generating light current. The addition of homocysteine will hinder the transfer of electrons, causing the cathode photocurrent to be decreased. The prepared sensor had good linear responses in the ranges of 10 ~ 100 nmol·L^-1 and 100 ~ 1000 nmol·L^-1, and the detection limit was 2.17 nmol·L^-1. The sensor also exhibited good stability and selectivity. The prepared cathode photoelectric sensor could sensitively and efficiently detect homocysteine in milk. The studied high-performance photoelectric active materials and chemical sensing platforms may be important for the design of other chemical sensing platforms and the development of PEC applications.