In Situ Growth of AuNPs on Glass Nanofibers for SERS Sensors.

It is challenging to fabricate plasmonic nanosensors on high-curvature surfaces with high sensitivity and reproducibility at low cost. Here, we report a facile and straightforward strategy, based on an in situ growth technique, for fabricating glass nanofibers covered by asymmetric gold nanoparticles (AuNPs) with tunable morphologies and adjustable spacings, leading to much improved surface-enhanced Raman scattering (SERS) sensitivity because of hotspots generated by the AuNP surface irregularities and adjacent AuNP coupling. First, nanosensors covered with uniform and well-dispersed citrate-capped spherical AuNPs were constructed using a polystyrene-b-poly(4-vinylpyridine) (PS-P4VP, with 33 mol % P4VP content and 61 kg/mol total molecular weight) block copolymer brush-layer templating method, and then, the deposited AuNPs were grown to asymmetric AuNPs. AuNP morphologies and hence the optical characteristics of AuNP-covered glass nanofibers were easily controlled by the choice of experimental parameters, such as the growth time and growth solution composition. In particular, tunable AuNP average diameters between about 40 and 80 nm with AuNP spacings between about 50 and 1 nm were achieved within 15 min of growth. The SERS sensitivity of branched AuNP-covered nanofibers (3 min growth time) was demonstrated to be more than threefold more intense than that of the original spherical AuNP-covered nanofibers using a 633 nm laser. Finite-difference time-domain simulations were performed, showing that the electric field enhancement is highest for intermediate AuNP diameters. Furthermore, SERS applications of these nanosensors for H2O2 detection and pH sensing were demonstrated, offering appealing and promising candidates for real-time monitoring of extra/intracellular species in vitro and in vivo.