Uniform Microgels Containing Agglomerates of Silver Nanocubes for Molecular Size‐Selectivity and High SERS Activity

• Published in: Small (Weinheim an der Bergstrasse, Germany) Germany), 2017-06, Vol.13 (23), p.n/a
• Main Authors: Kim, Dong Jae, Jeon, Tae Yoon, Park, Sung‐Gyu, Han, Hye Ji, Im, Sang Hyuk, Kim, Dong‐Ho, Kim, Shin‐Hyun
• Format: Article
• Language: English
• Subjects: Adhesives; Agglomerates; Agglomeration; Amplification; Aspirin; Chemical fingerprinting; Contamination; hydrogels; Metal surfaces; microfluidics; Microgels; Nanostructure; Nanotechnology; Permeability; Pretreatment; Raman spectra; Scattering; Selectivity; semipermeable; Sensitivity; Silver; Spectroscopy; Spectrum analysis; Surface chemistry; surface‐enhanced Raman scattering
• ISSN: 1613-6810; 1613-6829
• DOI: 10.1002/smll.201604048

Surface‐enhanced Raman scattering (SERS) is a promising technique for molecular analysis as the molecular fingerprints (Raman spectra) are amplified to detectable levels compared with common spectroscopy. Metal nanostructures localize electromagnetic field on their surfaces, which can lead to dramatic increase of Raman intensity of molecules adsorbed. However, the metal surfaces are prone to contamination, thereby requiring pretreatment of samples to remove adhesive molecules. To avoid the pretreatment and potentially achieve point‐of‐care (POC) analysis, we have developed SERS‐active microgels using the droplet‐microfluidic system. As the microgels are composed of water‐swollen network with consistent mesh size, they selectively allow diffusion of molecules smaller than the mesh, thereby excluding large adhesives. To render the microgels highly SERS‐active, we destabilize silver nanocubes to form agglomerates, which are embedded in the matrix of microgels. The nanogaps in the agglomerates provide high sensitivity in Raman measurement and size‐selective permeability of the microgel matrix obviates the pretreatment of samples. To validate the functions, we demonstrate the direct detection of Aspirin dissolved in whole blood without any pretreatment. Microgels containing agglomerates of silver nanocubes are microfluidically created to provide surface‐enhanced Raman scattering (SERS)‐active substrates. The microgels permit selective infusion of small molecules, and nanogaps among the nanocubes serve as hotspots for SERS. Therefore, the microgels can selectively analyze Raman spectra of small molecules dissolved in complex mixtures with high sensitivity in the absence of interruption from large adhesives.