Influence of Solvophobicity of Biphenol-Derived Small Surface Ligands on the Formation of Size-Controllable Gold Nanoparticle Vesicles.

The self-assembly of gold nanoparticles (GNPs) into gold nanoparticle vesicles (GNVs) has been a topic of significant interest in recent years. However, the formation mechanism of GNVs is still not fully understood. In this article, we report that the new oligo(ethylene glycol)-terminated biphenol ligands (OBLs) show different solubility in tetrahydrofuran (THF) depending upon the number of terminal ethylene glycol units, resulting in a differential solvophobicity. The fluorine-free OBLs have the ability to self-assemble with GNPs into GNVs driven by the solvophobic feature of the ligands. The size of GNVs can be precisely controlled by tuning the interparticle attraction through changes in the unit number of terminal ethylene glycol or the water content in THF. Time-dependent studies revealed that the vesicle formation process consists of two stages: the rapid generation of vesicles, followed by their fusion to form thermodynamically stable GNVs with a saturated size. These two rapid processes are primarily influenced by the pronounced solvophobic attraction exerted by the surface ligands.

Ultrasensitive Surface-Enhanced Raman Scattering Platform for Protein Detection via Active Delivery to Nanogaps as a Hotspot.

Surface-enhanced Raman scattering (SERS) is an attractive technique in molecular detection with high sensitivity and label-free characteristics. However, its use in protein detection is limited by the large volume of proteins, hindering its approach to the narrow spaces of hotspots. In this study, we fabricated a Au nanoTriangle plate Array on Gel (AuTAG) as an SERS substrate by attaching a Au nanoTriangle plate (AuNT) arrangement on a thermoresponsive hydrogel surface. The AuTAG acts as an actively tunable plasmonic device, on which the interparticle distance is altered by controlling temperature via changes in hydrogel volume. Further, we designed a Gel Filter Trapping (GFT) method as an active protein delivery strategy based on the characteristics of hydrogels, which can absorb water and separate biopolymers through their three-dimensional (3D) polymer networks. On the AuTAGs, fabricated with AuNTs modified with charged surface ligands to prevent the nonspecific adsorption of analytes to particles, the GFT method helped the delivery of proteins to hotspot areas on the AuNT arrangement. This combination of a AuTAG substrate and the GFT method enables ultrahigh sensitivity for protein detection by SERS up to a single-molecule level as well as a wide quantification concentration range of 6 orders due to their geometric advantages.

Spatially Uniform and Quantitative Surface-Enhanced Raman Scattering under Modal Ultrastrong Coupling Beyond Nanostructure Homogeneity Limits.

We developed a substrate that enables highly sensitive and spatially uniform surface-enhanced Raman scattering (SERS). This substrate comprises densely packed gold nanoparticles (d-AuNPs)/titanium dioxide/Au film (d-ATA). The d-ATA substrate demonstrates modal ultrastrong coupling between localized surface plasmon resonances (LSPRs) of AuNPs and Fabry-Pérot nanocavities. d-ATA exhibits a significant enhancement of the near-field intensity, resulting in a 78-fold increase in the SERS signal for crystal violet (CV) compared to that of d-AuNP/TiO2 substrates. Importantly, high sensitivity and a spatially uniform signal intensity can be obtained without precise control of the shape and arrangement of the nanoscale AuNPs, enabling quantitative SERS measurements. Additionally, SERS measurements of rhodamine 6G (R6G) on this substrate under ultralow adsorption conditions (0.6 R6G molecules/AuNP) show a spatial variation in the signal intensity within 3%. These findings suggest that the SERS signal under modal ultrastrong coupling originates from multiple plasmonic particles with quantum coherence.