Interference-free Detection of Caffeine in Complex Matrices Using a Nanochannel Electrode Modified with Binary Hydrophilic–Hydrophobic PDMS

In the present study, a novel electrochemical sensor for the direct detection of caffeine in the crude sample has been prepared by plasma-triggered polydimethylsiloxane (PDMS) deposition on the indium tin oxide electrodes supported with silica nanochannels. The deposited PDMS contains both the original hydrophobic and oxidized hydrophilic PDMS oligomers. Nanochannels modified with these two kinds of PDMS with opposite wettability only allow the passage of small amphiphilic molecules such as caffeine, while other molecules including hydrophilic, hydrophobic, and large ones were all rejected. With the excellent shielding properties, the modified nanochannel electrode exhibits excellent anti-interference and antifouling capability, which could be directly used for the detection of caffeine in real crude food such as tea, milk, coffee, and coke without sample pretreatments. Moreover, the modified electrode has good repeatability and stability. In contrast, severe interference was observed when conventional electrodes were used directly in these unprocessed samples. The linear ranges of caffeine were determined to be between 50 nmol/L and 700 μmol/L, with a limit of detection of 20 nmol/L. The developed sensor provides a very simple, rapid, and cost-effective way for the interference-free and fouling-free analysis of specific amphiphilic compounds and can be extended to a wide range of applications.