Open Cross-gap Gold Nanocubes with Strong, Large-Area, Symmetric Electromagnetic Field Enhancement for On-Particle Molecular-Fingerprint Raman Bioassays

J Am Chem Soc. 2024 May 22;146(20):14012-14021. doi: 10.1021/jacs.4c02099. Epub 2024 May 13.

Abstract

Plasmonic nanoparticles with an externally open nanogap can localize the electromagnetic (EM) field inside the gap and directly detect the target via the open nanogap with surface-enhanced Raman scattering (SERS). It would be beneficial to design and synthesize the open gap nanoprobes in a high yield for obtaining uniform and quantitative signals from randomly oriented nanoparticles and utilizing these particles for direct SERS analysis. Here, we report a facile strategy to synthesize open cross-gap (X-gap) nanocubes (OXNCs) with size- and EM field-tunable gaps in a high yield. The site-specific growth of Au budding structures at the corners of the AuNC using the principle that the Au deposition rate is faster than the surface diffusion rate of the adatoms allows for a uniform X-gap formation. The average SERS enhancement factor (EF) for the OXNCs with 2.6 nm X-gaps was 1.2 × 109, and the EFs were narrowly distributed within 1 order of magnitude for ∼93% of the measured OXNCs. OXNCs consistently displayed strong EM field enhancement on large particle surfaces for widely varying incident light polarization directions, and this can be attributed to the symmetric X-gap geometry and the availability of these gaps on all 6 faces of a cube. Finally, the OXNC probes with varying X-gap sizes have been utilized in directly detecting biomolecules with varying sizes without Raman dyes. The concept, synthetic method, and biosensing results shown here with OXNCs pave the way for designing, synthesizing, and utilizing plasmonic nanoparticles for selective, quantitative molecular-fingerprint Raman sensing and imaging applications.