# Application of Molecularly Imprinted Polymers in the Analysis of Waters and Wastewaters
## 5 Application of MIPs for the Detection of Different Classes of Contaminants
### Pesticides
#### 5.3.1 Insecticides
\begin{array}{c}52-1.3\times\\ 10^{3}\text{ nM}\end{array} \) & \(9.0\) nM & [97] \\ \hline \multirow{2}{*}{Glyphosate} & Py & Electro- & \multirow{2}{*}{-} & \multirow{2}{*}{DPV} & \multirow{2}{*}{Tap water} & \( \begin{array}{c}30-4.7\times\\ 10^{3}\text{ nM}\end{array} \) & \(1.6\) nM & [98] \\ \cline{2-10}  & Hexazinone & 2-VP & Bulk & - & DPV & River water & \( \begin{array}{c}0.019-0.11\\ \text{ nM}\end{array} \) & \(2.6\times 10^{-3}\) & [99] \\ \hline \multirow{2}{*}{Propazine} & MAA & MIP-HFs & - & HPLC-DAD & \begin{tabular}{c} Tap and river \\ water \\ \end{tabular}  & \( \begin{array}{c}0.1-25\\ \text{\mu E}^{-1}\end{array} \) & \( \begin{array}{c}0.03-0.1\\ \text{\mu E}^{-1}\end{array} \) & [100] \\ \cline{2-10}  & MAA & MIP-SPME & - & HPLC-DAD & Tap water & - & \( \begin{array}{c}0.02-\\ 0.030\\ \text{\mu E}^{-1}\end{array} \) & [101] \\ \hline \multirow{2}{*}{Paraquat} & Py & Electro- & \multirow{2}{*}{EBB} & DPV & Dam water & \( \begin{array}{c}5.0\times 10^{3}\\ -5.0\times 10^{4}\end{array} \) & \( \begin{array}{c}2.2\times 10^{2}\\ \text{ nM}\end{array} \) & [102] \\ \cline{2-10}  & & & & & & & & \\ \cline{2-10}  & & & & & & & \\ \cline{2-10}  & & & & & & & \\ \cline{2-10}  & & & & & & & \\ \cline{  
Gold microelectrodes modified using electropolymerized pyrrole (Py) were applied for the detection of chlororyrifos (CPF). Differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) techniques were used for measurements. The voltammograms show a decrease in the peak current value from 3.9 to 0.27 \(\mu\)A as CPF concentrations increased from 1 fM to 1 \(\mu\)M. This is a consequence of CPF rebinding at the cavities in the PPy matrix, which primarily occurs via hydrogen bonding between the N group of pyridine in CPF and the N\(-\)H group of PPy. Recovery from spiked cucumber and pomegranate ranged from 91 to 97% with an RSD of 5% [117]. Another study reports the use of GCE modified with carbon nitride nanotubes (C\({}_{3}\)N\({}_{4}\) NTs) coated with graphene quantum dots (GQDs) electrodeposited pyrrole for the detection of chlororyrifos (CPF). The sensor's applicability in wastewater samples showed a limit of detection of 2.0 \(\times\) 10\({}^{-3}\) nM, with a linear range of 1.0 \(\times\) 10\({}^{-2}\)-1 nM using SWV for electrochemical measurements. The results for electrochemical methods are much more sensitive compared to other chromatographic methods, as indicated by the very low LOD. Magnetic imprinted polymers were prepared and characterized for the detection of 12 organophosphorus pesticides OPPs. Methyl-parathion (MP) and/or quinalphos (QP) were chosen as templates for the synthesis of dual template or single-template MIPs. \begin{table}
\begin{tabular}{c c c c c c c c c} \hline \hline
**Pesticide** & **Analyte** & **Functional** & **Polymerization** & **Modifier** & **Analytical** & **Sample(s)** & **Linear** & **Limit of** & **Ref. ** \\  & & **Monomer** & **Method** & **Medifier** & **Technique(s)** & **Range** & **Detection** & **Ref. ** \\ \hline \multirow{8}{*}{Chlororyrifos} & \multirow{2}{*}{Chlororyrifos} & \multirow{2}{*}{MAA} & Bulk & - & DPV & River water & 0.1–1.0 \(\times\) & 4.1 mM & [104] \\  & & & Electro- & C\({}_{3}\)Na NTs, & GWV & Industrial & 1.0 \(\times\) & 2.0 \(\times\) 10\({}^{-3}\) & [105] \\  & & Py & polymerization & GQDs & wastewater & 10\({}^{-2}\)-1 nM & nM & \\  & & PATP &  
The polymer showed high affinity and good recognition for all twelve OPPs including quinalphos, isazophos, chlorporyrifos-methyl, chlorporyrifos, methidathion, triazophos, profenofos, fenthion, fenitroth, methyl-parathion, parathion, and paraoxon. GC-MS results were attained within 10 min of interaction with the different templates, with a limit of detection of 1.62-13.9 ng g\({}^{-1}\) and spiked recoveries of 81.5-113.4%. Linear calibration plots were found in the range 10-800 ng mL\({}^{-1}\), indicating the applicability of the developed polymers for rapid determination and high throughput analysis of multi-pesticide residues [118].