LSPR Sensing of Epithelial Cell Adhesion Molecules through Sphere and Cavity Plasmons of a Composite Ring Array of Poly[2-(dimethylamino)ethyl methacrylate]/Gold Nanoparticles

Self-organization facilitates the formation of specific structures as a result of constituent interactions. In this study, the bottom of a 600 nm hole array photoresist template, which was deposited with a hydrophobic atom transfer radical polymerization (ATRP) initiator, was wetted by treatment with oxygen plasma. After the removal of the photoresist template, ring patterns of the ATRP initiator were formed at the interface between the hydrophobic and wetting regions. Poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) was grafted from the ring array of the initiator to immobilize gold nanoparticles (AuNPs) as a uniform ring array on a silicon substrate via repeated swelling/shrinking cycles. The localized surface plasmon resonance (LSPR) peak of the PDMAEMA-AuNP hybrid ring (PAHR) red-shifted after 12 swelling/shrinking cycles. In comparison to gold nanoparticles, scalable gold nanorings can effectively develop a variety of nanostructures to design LSPR-based sensors and optimize the sensing accuracy and stability. To detect epithelial cell adhesion molecules (EpCAM) during the structural change from a ring to a disk, antiEpCAM was anchored onto the PAHR as a biosensor during swelling/shrinking. The coupling of antiEpCAM and EpCAM led to asymptotical convergence from rings to disks as well as blue shifts of the LSPR peaks. Linear correlation between the blue shift and EpCAM concentration showed a limit of detection of ∼27 pg mL^-1 and a linear range of 25-200 pg mL^-1 for the detection of EpCAM within 30 min. The simple method of combining lithography and plasma technology provides a versatile platform for developing the scalable ring structure of AuNPs for highly sensitive and selective biosensing.