Breaking the Affinity Limit with Dual-Phase-Accessible Hotspot for Ultrahigh Raman Scattering of Nonadsorptive Molecules.

For surface-enhanced Raman scattering (SERS) analysis, only analytes that can be absorbed spontaneously onto a noble metal surface can be detected effectively. Therefore, getting nonadsorptive molecules close enough to the surface has always been a key challenge in SERS analysis. Here absorbance measurements show that the liquid-interfacial array (LIA) does not adsorb or enrich benzopyrene (Bap) molecules, which lack effective functional groups that can interact with the noble metal surfaces. But the SERS intensity of 0.1 ppm Bap on the LIA is 10 times larger than that of 10 ppm Bap on traditional solid substrate, i.e., 3 orders of magnitude of enhancement. The LIA overcomes the restriction of affinity between Bap molecules and the metal surface, and the Bap molecules can easily enter nanogaps without steric hindrance. Furthermore, both adsorptive and nonadsorptive molecules were used to observe the SERS enhancement behavior on the LIA platforms. In multiple detection, competitive SERS signal changes could be observed between adsorptive and nonadsorptive molecules or between nonadsorptive and nonadsorptive molecules. A theoretical scheme was profiled for localized surface plasmon resonance (SPR) properties of the LIA. Finite difference-time domain (FDTD) simulation shows that the LIAs have biphasic and accessible asymmetric hotspots, and the electric field enhancement in the CHCl (O) phase is approximately four times larger than that of the water (W) phase. In addition, the position and relative strength of the electromagnetic field depend on the spatial position of gold nanoparticles (GNPs) relative to the liquid-liquid interface (LLI), i.e., when the GNP dimer is completely immersed in a certain phase, the electromagnetic field enhancement of the CHCl phase is approximately 7 times larger than that of the W phase. We speculate that dual-phase-accessible hotspots and the hydrophobic environment provided by CHCl are two important factors contributing to successful detection of four common polycyclic aromatic hydrocarbons (PAHs) with a detection limit of 10 ppb. Finally, the LIA platform successfully realizes simultaneous detection of multiple PAHs in both plant and animal oils with good stability. This study provides a new direction for the development of high-efficiency and practical SERS technology for nonadsorptive molecules.