z Analytical Chemistry
Computational Design and Electropolymerization of
Molecularly Imprinted Poly(p-Aminobenzoic-Acid-Co–
Dapsone) Using Multivariate Optimization for Tetradifon
Residue Analysis
Fatemeh Ganjeizadeh Rohani,
[a, b]
Alireza Mohadesi,
[c]
and Mehdi Ansari*
[a]
In this study, tetradifon as a non-electroactive pesticide was
measured by a new gold electrode modified with electro-
polymerized molecularly imprinted poly(para aminobenzoic
acid-co-4,4-diaminodiphenyl sulfone) (P-pABA-co-DDS). The
best available monomer was selected based on computational
design and then the polymer was developed in optimized
condition. Screening of various factors was performed by
Plackett–Burman design (PBD) and central composite design
(CCD) was utilized to select optimized condition. Under the
optimized condition, calibration curve of tetradifon on MIP/
gold electrode was constructed with a linear range of 0.05-
2.50 μM. The limit of detection (LOD) and limit of quantification
(LOQ) was found to be 0.014 and 0.047 μM, respectively. The
developed method showed good stability, repeatability, and
reproducibility, sensitivity and selectivity for tetradifon. The
developed method was applied to determine tetradifon in real
water samples.
1. Introduction
Pollution is an important issue that has hit the world today and
the study of environmental pollution has attracted attention of
many researchers. The pesticides which used in agriculture, are
considered as one of the most dangerous pollutants of the
environment. Pesticides remained in the environment can
seriously harm human health and cause environmental con-
tamination. Tetradifon (4-chlorophenyl 2,4,5-trichlorophenyl
sulfone) is an organochlorine insecticide which is broadly used
to control a wide range of phytophagous mites which showed
toxicity, mutagenicity and carcinogenicity in animals.
[1]
Deter-
mination of trace amounts of the pesticides in water and
agricultural products is very challenging in view of health and
regulatory issues. Many analytical methods such as GC, HPLC,
GC-MS, TLC and CE have been reported for reliable, cost
effective and fast residue analysis of tetradifon in the environ-
ment. Most chromatographic methods are time consuming,
complicated and expensive.
[2]
Modification of electrodes by
conducting polymers extensively used because of high stability,
great precision, sticking on the electrode surface, proper
control of thickness and ease of the chemical modification to
obtain a higher response.
Molecular imprinting polymers first put forward by Wulff
[3]
and Mosbach
[4]
has taken considerable attention to many areas
of biotechnology
[5]
and biochemistry.
[6]
Due to the wide variety
of complex real sample matrices including fruits, vegetable and
biological materials, the development of analytical approaches
allowing the detection of pesticide residue with high selectivity
and sensitivity constitute a challenging task. MIPs with high
molecular recognition potential are proven to be excellent
sorbents for pesticide detection from real samples. MIP could
not only help as detectors of pesticides but also as one step
clean-up sorbents of pesticide residues in the environment.
[7]
Sensors development based on MIP have been drawn huge
considerations of researchers in recent two decades. Among
the MIP synthesis methods for sensor development, the
electrochemical procedures are the easiest and inexpensive
methods.
[8]
MIP has been extensively used in electrochemical sensors in
various fields of application such as the environmental
pollution monitoring,
[9]
drug detection,
[8,10]
food contaminants
analysis.
[11]
Selectivity, during sample pretreatment, can be
obtained by using sorbent able to retain compounds by a
molecular recognition mechanism. Tetradifon as a common
pesticide has been analyzed by a wide variety of methods
including gas chromatography, high performance liquid chro-
matography, thin layer chromatography, capillary electropho-
resis and chemiluminescence sensing,
[12]
but there isn’t any
report regarding the analysis of tetradifon by an electro-
chemical sensor.
Computer softwares in molecular design eliminates con-
sumption of large amount of hazardous organic solvents that
are regularly used in trial and error methods. The computa-
[a] F. Ganjeizadeh Rohani, Prof. M. Ansari
Pharmaceutics Research Center, Institute of Neuropharmacology, Kerman
University of Medical Sciences, Kerman, Iran
E-mail: mansai@kmu.ac.ir
[b] F. Ganjeizadeh Rohani
Plant Protection Research Department, Kerman Agricultural and Natural
Resources Research and Education Center, AREEO, Kerman, Iran
[c] Dr. A. Mohadesi
Department of Chemistry, Payame Noor University, 19395-4697, Tehran,
Iran
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/slct.201902830
Full Papers DOI: 10.1002/slct.201902830
12236 ChemistrySelect 2019, 4,12236–12244 © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim