Molecularly imprinted polymer-based sensors for atrazine detection by electropolymerization of o-phenylenediamine

Abstract

A sensitive and selective atrazine (ATZ) electrochemical sensor was developed based on molecularly imprinted polymer (MIP). The density functional theory at B3LYP/6-31G (d, p) level and Gaussian 2009 package was used to calculate the interaction energy of template-monomers. The MIP sensing film was prepared by electropolymerization of o-phenylenediamine (o-PD) using ATZ as the template. Some factors affecting the activity of the sensor have been discussed. The performance of the sensor was characterized by cyclic voltammetry and differential pulse voltammetry.Under the optimal experimental conditions, the relative current change was linear to the concentration of ATZ in the range of 5.0×10 -9 to 1.4×10 -7 M with a detection limit of 1.0×10 -9 M. The result of selectivity experiment showed that imprint electrode has good response and selectivity towards ATZ. The proposed MIP-based sensor also showed a good stability and repeatability.

Recent Advances in Electrosynthesized Molecularly Imprinted Polymer Sensing Platforms for Bioanalyte Detection

“…Direct deposition of MIPs composed of poly(o-phenylenediamine) (PoPD) on gold electrodes has been employed for the preparation of sensors with high selectivity for furosemide [ 108 ] and atrazine [ 109 ]. Galvanostatic deposition of pyrrole in the presence of the antibiotic, sulfadimethoxine, was extensively studied by Turco et al [ 110 ].…”

3,4-Methylenedioxypyrovalerone (MDPV) Sensing Based on Electropolymerized Molecularly Imprinted Polymers on Silver Nanoparticles and Carboxylated Multi-Walled Carbon Nanotubes

“…Electropolymerization was performed in the presence of o -PD and MDPV, in an analogous manner to the development of other e-MIPs in literature [ 89 , 90 , 91 ]. o-PD is largely used to develop MIPs [ 90 , 92 , 93 , 94 , 95 , 96 , 97 , 98 ] due to its highly reactive properties (and ability to polymerize at room temperature, for similar reason is also commonly used as a derivatizing agent [ 99 , 100 , 101 ]. Interestingly it seems that even though a ‘linear’ poly( o -PD) (i.e., when both vicinal amino groups react [ 102 , 103 , 104 ]) is more stable and produced in larger quantities, it is the ‘ramified’ poly( o -PD) (i.e., when only one of the amino group reacts and the other is left free to further reactions [ 102 , 105 ]) that is responsible for the suitable interactions with the template/monomer [ 90 ].…”

“…It has been long discussed that the formation of the pre-polymerization complex between the analyte and the building monomers in solution is the driving force of the molecular imprinting process [ 93 , 107 , 108 , 109 ]. The theoretical study of such a process, for its part, requires a good description of the pre-polymerization complex, but also of the potential energy surface (PES) of the interaction between the analyte and the monomers, which can originate a wide range of different complexes and conformers.…”

The Use of Computational Methods for the Development of Molecularly Imprinted Polymers

“…Investigations involving template–monomer complex studies have employed different methods, basis sets and levels of theories on several occasions. The majority of these studies employed DFT methods [ 124 , 131 , 132 , 133 , 134 , 135 , 136 , 137 , 138 , 139 , 140 , 141 , 142 , 143 , 144 , 145 , 146 , 147 , 148 , 149 , 150 , 151 , 152 , 153 , 154 , 155 , 156 , 157 , 158 , 159 , 160 , 161 , 162 , 163 , 164 , 165 , 166 , 167 , 168 , 169 , 170 , 171 , 172 , 173 , 174 , 175 , 176 , 177 , 178 , 179 , 180 ,…”