Polyvinylidene difluoride film with embedded poly(amidoamine) modified graphene oxide for extraction of chlorpyrifos and diazinon.

An effective, sensitive, relatively fast, and cost-effective method was developed to determine two types of selected organophosphorus pesticides (OPPs) including diazinon and chlorpyrifos in apple, peach, and four different water samples (river, sea, well, and agriculture wastewater samples) through applying poly(amidoamine)@graphene oxide-reinforced polyvinylidene difluoride thin-film microextraction (PAMAM@GO-PVDF-TFME). The extracted analytes were desorbed via organic solvent and determined using high-performance liquid chromatography-ultraviolet detection (HPLC-UV). The strong interactions between the sorbent and selected analytes (coordination bonds, intermolecular hydrogen bonding, π-π interactions, and hydrophobic effects) made this TFME capable of high extraction performance and capacity. Several factors involved in the PAMAM@GO-PVDF-TFME experiments such as desorption volume, desorption time, sample pH, extraction time, and stirring rate were screened via Plackett-Burman design and then optimized through Box-Behnken design with the purpose of reaching the highest extraction efficiency. The above method showed a good linear range (0.5-500 μg L and 1-500 μg L) with the coefficient of determination better 0.9944, low limits of determination (0.12 and 0.20 μg L), good enrichment factors (99 and 98), acceptable extraction recoveries (99 and 98%), and good spiking recoveries (90-98%) under the optimized condition at three different spike levels for chlorpyrifos and diazinon, respectively. The results confirmed that the presented method would be promising for the determination of various types of these pesticides in environmental and beverage samples.