Study On Molecularly Imprinted Photoelectrochemical Sensor For Determination Of Four Antitumor Active Molecules

In order to realize the simple,rapid and efficient detection of the four antitumor drug active molecules,colchicine（COL）,podophyllotoxin（PPT）,artemisinin（ART）and paclitaxel（PTX）,prepared four molecularly imprinted photoelectrochemical sensors for four antitumor drug active molecules based on four different optoelectronic materials.The above four sensors were characterized by various methods:electron microscope（EM）、X-ray diffraction spectroscopy、chronoamperometry（i-t）、cyclic voltammetry（CV）、alternating current impedance spectroscopy（EIS）and so on.A opto-electric measurement method for the four antitumor drug active molecules of podophyllotoxin,colchicine,artemisinin and paclitaxel in real samples based on the prepared sensor was established.The details are as follows:1、The study of COL molecular imprinted photoelectrochemical sensor modified with the TiO₂powder was calcined at the 500℃.Made TiO₂has better photoelectrochemical performance by optimizing the calcination temperature of titanium dioxide,and the calcination at 500℃for 1 h is the optimal calcination condition,named 500℃-TiO₂.The 500℃-TiO₂/FTO electrode was prepared by drop coating.Using COL as the template molecule and allylurea（NAU）as the functional monomer.Then the in-situ polymerization method was employed to prepare the COL molecularly imprinted polymer film photoelectrochemical sensors based on calcined TiO₂（COL-MIM/500℃-TiO₂/FTO）.Under optimized conditions,the detection range of the sensor is 4.0×10^-10～1.0×10^-7mol/L and 1.0×10^-7～1.0×10^-5mol/L.The detection limit of the sensor is 1.5×10^-10mol/L（S/N=3）.In the COL test of human whole blood,the recovery rate of standard addition is between 92.0%～105.6%and the RSD is less than 5.1%.2、The study of PPT molecular imprinted photoelectrochemical sensor modified with TiO₂-reduced graphene oxide composite.Firstly,reduced graphene oxide（rGO）and titanium dioxide（TiO₂）were doped together through a hydrothermal reaction in this experiment.The excellent electrical conductivity of rGO was used to increase the conductivity of TiO₂.At the same time,the TiO₂attached to the rGO could prevent the rGO from agglomerating together.And the formation of an effective electron transfer channel between the two,makes the TiO₂@rGO composite have better photoelectrochemical performance.The TiO₂@rGO/ITO electrode was prepared by drop coating.Using PPT as the template molecule andα-methacrylic acid（MAA）as the functional monomer.Then the in-situ polymerization method was employed to prepare the PPT molecularly imprinted polymer film photoelectrochemical sensors based on TiO₂doped with rGO（PPT-MIM/TiO₂@rGO/ITO）.The detection range of the sensor is 1.0×10^-9～1.0×10^-5mol/L.The detection limit of the sensor is 2.6×10^-10mol/L（S/N=3）.In the PPT test of human whole blood,the recovery rate of standard addition is between 97.4%～106.0%and the RSD is less than 4.8%.3、The study of ART molecular imprinted photoelectrochemical sensor modified with MoS₂@Au composite.Sodium citrate was used to reduce chloroauric acid to prepare gold nanoparticles,then the MoS₂and Au were doped together by ultrasonic and stirring.The gold nanoparticles were used to decorate molybdenum disulfide to improve the photoelectrochemical performance of the MoS₂@Au composite.The MoS₂@Au/FTO electrode was prepared by drop coating.Using ART as the template molecule and acrylamide（AM）as the functional monomer.Then the in-situ polymerization method was employed to prepare the ART molecularly imprinted polymer film photoelectrochemical sensors based on MoS₂doped with Au（ART-MIM/MoS₂@Au/FTO）.The detection range of the sensor is 4.0×10^-9～1.0×10^-5mol/L.The detection limit of the sensor is 1.3×10^-9mol/L（S/N=3）.In the ART test of veterinary artemisia annua powder extract,the recovery rate of standard addition is between 96.8%～108.0%and the RSD is less than 4.8%.4、The study of PTX molecular imprinted photoelectrochemical sensor modified with the Tp-BTD-ABC COF.In the experiment,the covalent organic frameworks（COFs）Tp-BTD-ABC COF synthesized by this subject was used as the photoelectric sensitizing material.The Tp-BTD-ABC/ITO electrode was prepared by drop coating.Using PTX as the template molecule and 2-vinylpyridine（2-VP）as the functional monomer.Then the in-situ polymerization method was employed to prepare the PTX molecularly imprinted polymer film photoelectrochemical sensors based on Tp-BTD-ABC COF/ITO（PTX-MIM/Tp-BTD-ABC/ITO）.The detection range of the sensor is 3.0×10^-10～4.0×10^-7mol/L.The detection limit of the sensor is 1.3×10^-10mol/L（S/N=3）.In the PTX test of human whole blood,the recovery rate of standard addition is between 94.4%～108.8%and the RSD is less than 5.2%.