Size-controllable colloidal Ag nano-aggregates with long-time SERS detection window for on-line high-throughput detection

Making metal nanoparticle aggregates is a common way to improve surface-enhanced Raman scattering (SERS) enhancement via the formation of hot spots between nanoparticles. Here, we propose a "freeze-thaw-ultrasonication" method to obtain stable colloidal Ag nano-aggregates (AgNAs) with controllable sizes, which can remain stable for a few days. Compared with other method using aggregation reagents (e.g., organic molecules and salt), this method can maintain metal surface charges and adsorption affinity, which ensures the excellent SERS stability and sensitivity. The SERS detection window during the experiment can reach more than 25 min, which makes it a prerequisite for accurate SERS detection during a long-time range. Combining the obtained stable AgNAs with microfluidic devices, we established a sequential SERS on-line continuous detection method for the high-throughput detection of multiplex samples. The UV-Fenton degradation process of methylene blue (MB) is continuously on-line monitored through this platform, which is more sensitive than the UV-Vis Spectrum. Moreover, we have realized the sensitive and accurate detection of 5-nitro-8-hydroxyquinoline (5-NQ) with antibacterial and anticancer activities based on chloride-functionalized silver, which paved a way for SERS high-throughput analysis in bioanalysis and other fields.