Ultrasound-promoted covalent functionalization of CNFs with thermo-sensitive PNIPAM via "grafting-from" strategy for on/off switchable electrochemical determination of clothianidin.

A thermo-sensitive poly (N-isopropylacrylamide) covalently grafted carbon nanofibers (CNFs-g-PNIPAM) was designed and synthesized via ultrasonic "grafting-from" strategy for the first time. CNFs-g-PNIPAM could well perform the reversible regulation of hydrophilic/hydrophobic states in aqueous solution upon the switching of the temperature signal. Such distinctive property, CNFs-g-PNIPAM modified glassy carbon electrode (CNFs-g-PNIPAM/GC electrode) shows "on/off" switchability and temperature-tunable electrocatalytic activity towards clothianidin (CLD) that can be stimulated by external temperature. Cyclic voltammetry of CLD at the CNFs-g-PNIPAM/GC electrode displayed higher peak current at 25 °C showing the "on" state; at 40 °C, the peak current was significantly suppressed, showing the "off" state. The CNFs-g-PNIPAM/GC electrode reveal the better electrochemical performance of 'on/off' switching effect compared to virgin PNIPAM, due to the large surface area, good electron-transfer, and an intrinsic property of introduced CNFs. Moreover, this switchable sensing platform allows determining CLD in a good sensitivity (2.32 µA µM-1 cm-2) with a low detection limit (LOD) of 0.03 µM at 25 °C compared to 40 °C (LOD = 1.3 µM). Besides, this method was successfully applied to the determination of CLD in spiked apple extract and lake water samples. The switchable electrocatalytic performance of CNFs-g-PNIPAM/GC electrode may greatly enhance the flexibility of its application in the area of electrochemical sensor and electrocatalysis.