Surface-Enhanced Raman Spectroscopy on Liquid Interfacial Nanoparticle Arrays for Multiplex Detecting Drugs in Urine.

Abstract

The design and application of liquid interfacial plasmonic platform is still in its infancy but is an exciting topic in tunable optical devices, sensors, and catalysis. Here, we developed an interfacial surface-enhanced Raman scattering (SERS) platform through the large-scale self-assembly of gold nanoparticle (GNP) arrays at the cyclohexane (CYH)/water interface for detecting trace drug molecules in the urine of humans. The molecules extracted by the CYH phase from a urine sample were directly localized into the self-organized plasmonic hotspots, yielded excellent Raman enhancement, and realized the substrate-free interfacial SERS detection. Synchrotron radiation small-angle X-ray scattering (SR-SAXS) experiments reveals a good uniformity of approximately 2-3 nm interparticle distance in the GNP arrays. SERS colocalization experiments demonstrated that amphetamine molecules of different concentration levels could be loaded into the interfacial GNP arrays and realized the coassembly together with nanoparticles at the liquid/liquid interface. Interfacial GNP arrays with dynamic nanogaps in liquid interfacial structure can make surrounding molecules easily diffuse into the nanogaps. In contrast, the fixed GNP arrays on Si wafer were more irregular, such as multilayer stack, random aggregates, and voids, during the drying process. When the drugs directly participate in the self-assembly process, it becomes easier for analytes diffusing into the nanogaps of GNP arrays, produces a concentration effect, and amplified the SERS sensitivity. This feature also enables molecules to be adsorbed evenly in the arrays and makes a more uniform distribution of both the analytes and GNPs in the liquid interface and realizes the significant increase in signal reproducibility. Interfacial SERS produced a standard deviation of 12.5% at 1001 cm(-1) peak of methamphetamine (MAMP) molecules under the concentration of 1 ppm, implying a good reproducibility. Moreover, dual-analyte detection at organic and aqueous phases was also realized and confirmed a good capability for analytes detection by liquid interfacial SERS platform, which promises nonengineering detection of analytes dissolved in often-inaccessible environments.