RESUMEN
The sensitive detection of viruses is key to preventing the spread of infectious diseases. In this study, we develop a silica-encapsulated Au core-satellite (CS@SiO2) nanotag, which produces a strong and reproducible surface-enhanced Raman scattering (SERS) signal. The combination of SERS from the CS@SiO2 nanotags with enzyme-linked immunosorbent assay (ELISA) achieves a highly sensitive detection of SARS-CoV-2. The CS@SiO2 nanotag is constructed by assembling 32 nm Au nanoparticles (AuNPs) on a 75 nm AuNP. Then the core-satellite particles are encapsulated with SiO2 for facile surface modification and stability. The SERS-ELISA technique using the CS@SiO2 nanotags provides a great sensitivity, yielding a detection limit of 8.81 PFU mL-1, which is 10 times better than conventional ELISA and 100 times better than lateral flow assay strip method. SERS-ELISA is applied to 30 SARS-CoV-2 clinical samples and achieved 100% and 55% sensitivities for 15 and 9 positive samples with cycle thresholds < 30 and > 30, respectively. This new CS@SiO2-SERS-ELISA method is an innovative technique that can significantly reduce the false-negative diagnostic rate for SARS-CoV-2 and thereby contribute to overcoming the current pandemic crisis.
RESUMEN
Plasmonic nanoparticles exhibit unique properties that distinguish them from other nanomaterials, including vibrant visible colors, the generation of local electric fields, the production of hot charge carriers, and localized heat emission. These properties are particularly enhanced in the narrow nanogaps formed between nanostructures. Therefore, creating nanogaps in a controlled fashion is the key to achieving a fundamental understanding of plasmonic phenomena originating from the nanogaps and developing advanced nanomaterials with enhanced performance for diverse applications. One of the most effective approaches to creating nanogaps is to assemble individual nanoparticles into a clustered structure. In this study, we present a fast, facile, and highly efficient method for preparing core@satellite (CS) nanoassembly structures using gold nanoparticles of various shapes and sizes, including nanospheres, nanocubes (AuNCs), nanorods, and nanotriangular prisms. The sequential assembly of these building blocks on glass substrates allows us to obtain CS nanostructures with a 100% yield within 4 h. Using 9 different building blocks, we successfully produce 16 distinct CS nanoassemblies and systematically investigate the combinations to search for the highest Raman enhancement. We find that the surface-enhanced Raman scattering (SERS) intensity of AuNC@AuNC CS nanoassemblies is 2 orders of magnitude larger than that of other CS nanoassemblies. Theoretical analyses reveal that the intensity and distribution of the electric field induced in the nanogaps by plasmon excitation, as well as the number of molecules in the interfacial region, collectively contribute to the unprecedentedly large SERS enhancement observed for AuNC@AuNC. This study not only presents a novel assembly method that can be extended to produce many other nanoassemblies but also identifies a highly promising SERS material for sensing and diagnostics through a systematic search process.
RESUMEN
The plasmonic properties of gold nanoparticles (AuNPs), such as color tunability, electric field generation, hot carrier generation, and localized heating, are significantly enhanced in the nanogaps between AuNPs. Therefore, the creation and control of nanogaps are key to developing advanced plasmonic nanomaterials. Most AuNP nanoassemblies, including dimers, trimers, and core-satellites, have a single type of nanogap within the assembly. In this study, we construct core-satellite-satellite (CSS) hierarchical, fractal-like nanostructures featuring two types of nanogaps, namely first generation nanogaps (Gap1) between the core and first satellite (Sat1) AuNPs and second generation nanogaps (Gap2) between Sat1 and second satellite (Sat2) AuNPs. The sequential and alternating immersion of glass slides in different-sized AuNPs and linkers forms CSS with perfect yield. The UV-vis spectroscopy, combined with charge density distribution calculations, reveals the nature of the plasmon coupling between the AuNPs that constitute CSS nanoassemblies. The plasmon coupling can be tuned by independently varying Gap1 and Gap2. Furthermore, we explore the electric field amplification in Gap1 and Gap2 by comparing the surface-enhanced Raman scattering signal intensity selectively from each nanogap. This new type of nanostructure provides a great flexibility to control and enhance the plasmonic properties of noble metal nanoparticles.
RESUMEN
Boronic acids are the key compounds in Suzuki coupling reactions and in the detection of monosaccharides. The C-B bond cleavage deboronation is an important side reaction that lowers the Suzuki coupling reaction yield and even disables saccharide detection. Here, we report that protodeboronation occurs for 4-mercaptophenylboronic acid (MPBA) within narrow nanogaps between gold nanoparticles (AuNPs) and planar gold substrates. The irradiation of such nanoparticle-on-mirror (NPoM) systems at 785 nm drives the protodeboronation reaction to form benzenethiol (BT). Wavelength-dependence experiments, combined with dark-field single-particle scattering spectroscopy, reveal that excitation of the bonding dipole plasmon mode of the NPoM leads to the best efficiency. Among the excited plasmon decay pathways, the generation of hot charge carriers induces the protodeboronation of MPBA. The possibility of plasmonic thermal reactions is ruled out because external heating of the substrates does not cause the reaction to take place. A comparison of the reaction yield under ambient, Ar, and oxygen gas conditions reveals that hot charge carriers directly transfer to MPBA, which subsequently produces BT, but the presence of oxygen promotes the reaction by opening another hot-electron transfer channel. The protodeboronation reaction of MPBA is an important addition to the catalog of plasmon-driven chemical reactions, not only because the reaction is relevant to organic and analytical chemistry but also because it deepens our understanding of the hot carrier dynamics at the interface between plasmonic nanoparticles and molecules.
RESUMEN
Hot-electron chemistry at gold nanoparticle (AuNP) surfaces has received much attention recently because its understanding provides a basis for plasmonic photocatalysis and photovoltaics. Nonradiative decay of excited surface plasmons produces energetic hot charge carriers that transfer to adsorbate molecules and induce chemical reactions. Such plasmon-driven reactions, however, have been limited to a few systems, notably the dimerization of 4-aminobenzenethiol to 4,4'-dimercaptoazobenzene. In this work, we explore a new class of plasmon-driven reactions associated with a unimolecular bond cleavage process. We unveil the mechanism of the decarboxylation reaction of 4-mercaptobenzoic acid and extend the mechanism to account for the ß-cleavage reaction of 4-mercaptobenzyl alcohol. Combining the construction of well-controlled nanogap systems and sensitive Raman spectroscopy with methodical changes of experimental conditions (laser wavelengths, interface materials, pH, ambient gases, etc.), we track the hot charge carriers from the formation to the transfer to reactants, which provides insights into how plasmon excitation eventually leads to the C-C bond cleavage of the molecules in the nanogap.