Electropolymerization of Metallophthalocyanines Carrying Redox Active Metal Centers and their Electrochemical Pesticide Sensing Application

Abstract

In this study, modified electrodes were constructed with the electropolymerization of metallophthalocyanines (MPcs) carrying redox active metal cations and electropolymerizable substituents. Then these electrodes were tested as selective and sensitive electrochemical pesticide sensors. Incorporation of the redox active Co(II) (CoPc(MOR‐NAF)), Cl–Mn(III) (MnPc(MOR‐NAF)), and Ti(IV)O (TiOPc(MOR‐NAF)) metal cations into Pc cavity increased the redox activity of Pc ring. Moreover, redox active and electropolymerizable 5‐{[(1E)‐(4‐morpholin‐4‐ylphenyl)methylene]amino}‐1‐naphthoxy substituents (MOR‐NAF) on the Pc ring triggered coating of the complexes on the electrode surface with the electropolymerization reactions. Therefore, modified electrodes GCE/MPc(MOR‐NAF) were constructed with the electropolymerizations of MPcs. These electrodes illustrated reasonable redox activity and conductivity for the potential applications in different fields of the electrochemical technologies. Pesticide sensing measurements indicated that changing the metal center of the complexes significantly altered their sensing activities. Among the complexes, GCE/CoPc(MOR‐NAF) electrode behaved as the most sensitive and selective electrode and it sensed the parathion with good selectivity and sensitivity. GCE/CoPc(MOR‐NAF) electrode showed a wider linear range (0.075‐5.75 μmoldm−3) and smaller LOD (0.025 μmoldm−3) and higher sensitivity (3.46 Acm−2M−1) for the parathion sensing. Although GCE/TiOPc(MOR‐NAF) electrode also sensed the parathion with a high sensitivity, its selectivity was poor and the linear range of this sensing was very narrow. Differently GCE/Cl–MnPc(MOR‐NAF) electrode only sensed eserine with reasonably sensitivity.

Construction of Modified Electrodes with Click Electrochemistry Based on the Hybrid of 4-Azido Aniline and Manganese Phthalocyanine and Electrochemical Pesticide Sensor Applications

“…In our previous papers, we have reported various selective pesticide sensors based on MPcs. 4,20 For instance, the electropolymerized film of CoPc(ma) based sensor detected the fenitrothion with good selectivity and sensitivity. 4 In another study, [CoPc(ea)], [Cl-MnPc(ea)], and Ti(IV)O [TiOPc(ea)] based sensors were tested as the pesticide sensors and it was found that GCE/CoPc(ea) electrode detected the fenitrothion pesticide, GCE/MnClPc(ea) electrode detected eserine and GCE/TiOPc(ea) electrode detected parathion with good selectivity and high sensitivity and small LOD values of 8.88 10 −8 , 6.43 10 −7 , 8.64 10 −7 moldm −3 respectively.…”

“…7,[15][16][17][18] Recently we have tested various MPcs as electrocatalysts and electrochemical sensors. 7,[19][20][21][22] It was well reported in these applications that besides the functionality of MPcs, electrode modification techniques significantly influenced the activity of the sensors. MPc films on a substrate could be prepared with different techniques, such as spin coating, physical vapor deposition, molecular beam deposition, Langmuir-Blodgett deposition (LB), electropolymerization, electrodeposition or covalent anchoring.…”

Recent advances in phthalocyanines for chemical sensor, non-linear optics (NLO) and energy storage applications

“…Linear range, sensitivities and LODs obtained from different sensors for Cl2 gas and pesticides: fenitrothion, diazinon and eserine. ( [59], [60], [61], [62], [63], [64], [65], [66], [67], [68], [69], Cl2 is recognised as a toxic gas with an occupational exposure limit of 500 ppb [71]. Exposure to Cl2 gas for an average of six hours can lead to respiratory complications and sensory irritation [72].…”

Synthesis of nonperipherally tetra-[5-(diethylamino)-2-formylphenoxy] substituted metallophthalocyanines and their electrochemistry

“…In addition, their unique electronic and chemical properties, physical and optical properties, as well as their chemical flexibility of phthalocyanines allow preparation of variety of related structures and diverse applications ranging from industrial to biological areas [3,4]. Phthalocyanines have been used in different areas such as photodynamic therapy [5,6], nonlinear optical materials [7], electrochemical sensors [8,9], biosensors [10], solar cells [11,12], light-emitting decives [13], liquid crystals [14], electrocatalyts [15], electropolymerization [16,17]. The solubility of unsubstituted phthalocyanines is very low in organic solvents.…”