Biomass-assisted fabrication of rGO-AuNPs as surface-enhanced Raman scattering substrates for in-situ monitoring methylene blue degradation.

Surface-Enhanced Raman spectroscopy for Point-of-Care Bioanalysis: From lab to field

Surface-enhanced Raman scattering technology plays a prominent role in spectroscopy. By introducing plasmonic metals and photonic crystals as a substrate, SERS signals can achieve further enhancement. However, the conventional doping preparation methods of these SERS substrates are insufficient in terms of metal-loading capacity and the coupling strength between plasmonic metals and photonic crystals, both of which reduce the SERS activity and reproducibility of SERS substrates. In this work, we report an approach combining spin-coating, surface modification, and in situ reduction methods. Using this approach, a photonic crystal array of SiO2@Au core–shell structure nanoparticles was prepared as a SERS substrate (SiO2@Au NP array). To study the SERS properties of these substrates, Rhodamine 6G was employed as the probe molecule. Compared with a Au-SiO2 NP array prepared using doping methods, the SiO2@Au NP array presented better SERS properties, and it reproduced the SERS spectra after one month. The detection limit of the Rhodamine 6G on SiO2@Au NP array reached 1 × 10−8 mol/L; furthermore, the relative standard deviation (9.82%) of reproducibility and the enhancement factor (1.51 × 106) were evaluated. Our approach provides a new potential option for the preparation of SERS substrates and offers a potential advantage in trace contaminant detection, and nondestructive testing. 

Preparation of SiO2@Au Nanoparticle Photonic Crystal Array as Surface-Enhanced Raman Scattering (SERS) Substrate

Surface-enhanced Raman scattering (SERS) has been widely reported to improve the sensitivity of Raman spectra. Ordinarily, the laser is focused on the sample to measure the Raman spectrum. The size of the focused light spot is comparable with that of micro-nano structures, and the number of micro-nano structures contained in the light spot area (defined as duty cycle) will severely affect the spectrum intensity. In this study, flower-like silver nanostructures were fabricated with a soft lyotropic liquid crystal template in order to investigate the effect of duty cycle. They were observed under a scanning electron microscope, and their spectrum enhancement factor was computed with the obtained Raman spectrum. Then, their duty cycles were measured using a SERS substrate at different locations. A formula was derived to represent the relation between the duty cycle of the nanoflowers and the Raman spectral intensity. This work could promote the actual applications of SERS in high-sensitivity spectrum testing.

Effect of the Duty Cycle of Flower-like Silver Nanostructures Fabricated with a Lyotropic Liquid Crystal on the SERS Spectrum.

The combination of plasmonic metals and photonic crystal (PC) structure is considered to have potential for further enhancement of the surface-enhanced Raman scattering (SERS) effect in comparison with conventional metal SERS substrates. Many studies have suggested that SERS signals probably suffer from an often-neglected effect of strong surface plasmon resonance (SPR)-induced photothermal heating during SERS detection. Herein, we have discovered that the photothermal heating problem arises in a traditional hybrid substrate that is prepared by doping plasmonic Au nanoparticles (NPs) into the voids of an opal PC (Au-PC). This happens mainly because excess Au agglomerates formed by non-uniformly distributed Au NPs can cause a strong SPR effect under laser illumination. To fully address this issue, we have employed an improved hybrid substrate that is fabricated by substituting Au NPs in Au-PC with an Au-loaded magnetic framework (AuMF). The AuMF can effectively prevent the aggregation of Au NPs and ensure sufficient hot spots for SERS. This novel substrate prepared by doping AuMFs into a PC (AuMF-PC) was free of strong photothermal heating and showed high SERS intensity and reproducibility of the SERS signal compared with Au-PC. For practical applications, we have demonstrated AuMF-PC as an appropriate candidate for the SERS assay of the trace thiol pesticide thiram, and it enables recycling and reuse to achieve low cost.

Coupling Au-loaded magnetic frameworks to photonic crystal for the improvement of photothermal heating effect in SERS

Preparation of a monolayer array of silica@gold core-shell nanoparticles as a SERS substrate

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Preparation of a monolayer array of silica@gold core-shell nanoparticles as a SERS substrate