Surface-Enhanced Raman Spectroscopy: Current Understanding, Challenges, and Opportunities
Hao Ma,
Si-Qi Pan,
Wei-Li Wang
et al.
Abstract:While surface-enhanced Raman spectroscopy (SERS) has experienced substantial advancements since its discovery in the 1970s, it is an opportunity to celebrate achievements, consider ongoing endeavors, and anticipate the future trajectory of SERS. In this perspective, we encapsulate the latest breakthroughs in comprehending the electromagnetic enhancement mechanisms of SERS, and revisit CT mechanisms of semiconductors. We then summarize the strategies to improve sensitivity, selectivity, and reliability. After a… Show more
“…Recently, research efforts have been directed toward developing analytical methods to detect smaller nanoplastic contamination in the environment. − However, sensitive detection of nanoplastics with low concentration levels in complex environmental samples remains elusive due to the smaller size fraction of particulate nanoplastics . Surface-enhanced Raman scattering (SERS) spectroscopy has emerged as a powerful, nondestructive spectroscopy technique that offers sensitive identification of analytes with high sensitivity and the ability to identify molecular fingerprints. − To achieve high sensitivity and good signal reproducibility as well as stability of the SERS substrates, various strategies have been developed. − In particular, “hotspot” engineering in the gaps of plasmonic NPs such as Ag, Au, and Cu, − designing three-dimensional (3D) plasmonic nanostructures, , plasmonic NPs on 2D materials such as graphene, MoS 2 , Mxane, and their heterostructures have been widely studied. − Nevertheless, the fabrication of a SERS substrate with maximum “hotspots” density for a highly reproducible signal and implementation of the plasmonic NP substrates in direct detection of target analytes in complex environments is still elusive …”
Nanoplastics pollution has led to a severe environmental crisis because of a large accumulation of these smaller nanoplastic particles in the aquatic environment and atmospheric conditions. Detection of these nanoplastics is crucial for food safety monitoring and human health. In this work, we report a simple and eco-friendly method to prepare a SERS-substrate-based nanoporous Ag nanoparticle (NP) film through vacuum thermal evaporation onto a vacuum-compatible deep eutectic solvent (DES) coated growth substrate for quantitative detection of nanoplastics in environmental samples. The nanoporous Ag NP films with controlled pores were achieved by the soft-templating role of DESs over the growth substrate, which enabled the selfassembly of deposited Ag NPs over the surface of DES. The optimized nanoporous Ag substrate provides high sensitivity in the detection of analyte molecules, crystal violet (CV), and rhodamine 6G (R6G) with a limit of detection (LOD) up to 1.5 × 10 −13 M, excellent signal reproducibility, and storage stability. Moreover, we analyzed quantitative SERS detection of polyethene terephthalate (PET, size of 200 nm) and polystyrene (PS, size of 100 nm) nanoplastics with an LOD of 0.38 and 0.98 μg/mL, respectively. In addition, the SERS substrate efficiently detects PET and PS nanoplastics in real environmental samples, such as tap water, lake water, and diluted milk. The enhanced SERS sensing ability of the proposed nanoporous Ag NP film substrate holds immense potential for the sensitive detection of various nanoplastic contaminants present in environmental water.
“…Recently, research efforts have been directed toward developing analytical methods to detect smaller nanoplastic contamination in the environment. − However, sensitive detection of nanoplastics with low concentration levels in complex environmental samples remains elusive due to the smaller size fraction of particulate nanoplastics . Surface-enhanced Raman scattering (SERS) spectroscopy has emerged as a powerful, nondestructive spectroscopy technique that offers sensitive identification of analytes with high sensitivity and the ability to identify molecular fingerprints. − To achieve high sensitivity and good signal reproducibility as well as stability of the SERS substrates, various strategies have been developed. − In particular, “hotspot” engineering in the gaps of plasmonic NPs such as Ag, Au, and Cu, − designing three-dimensional (3D) plasmonic nanostructures, , plasmonic NPs on 2D materials such as graphene, MoS 2 , Mxane, and their heterostructures have been widely studied. − Nevertheless, the fabrication of a SERS substrate with maximum “hotspots” density for a highly reproducible signal and implementation of the plasmonic NP substrates in direct detection of target analytes in complex environments is still elusive …”
Nanoplastics pollution has led to a severe environmental crisis because of a large accumulation of these smaller nanoplastic particles in the aquatic environment and atmospheric conditions. Detection of these nanoplastics is crucial for food safety monitoring and human health. In this work, we report a simple and eco-friendly method to prepare a SERS-substrate-based nanoporous Ag nanoparticle (NP) film through vacuum thermal evaporation onto a vacuum-compatible deep eutectic solvent (DES) coated growth substrate for quantitative detection of nanoplastics in environmental samples. The nanoporous Ag NP films with controlled pores were achieved by the soft-templating role of DESs over the growth substrate, which enabled the selfassembly of deposited Ag NPs over the surface of DES. The optimized nanoporous Ag substrate provides high sensitivity in the detection of analyte molecules, crystal violet (CV), and rhodamine 6G (R6G) with a limit of detection (LOD) up to 1.5 × 10 −13 M, excellent signal reproducibility, and storage stability. Moreover, we analyzed quantitative SERS detection of polyethene terephthalate (PET, size of 200 nm) and polystyrene (PS, size of 100 nm) nanoplastics with an LOD of 0.38 and 0.98 μg/mL, respectively. In addition, the SERS substrate efficiently detects PET and PS nanoplastics in real environmental samples, such as tap water, lake water, and diluted milk. The enhanced SERS sensing ability of the proposed nanoporous Ag NP film substrate holds immense potential for the sensitive detection of various nanoplastic contaminants present in environmental water.
Strengthening the interaction between the target and SERS substrate is crucial for sensitive SERS detection; we thereby explored the molecular structure-dependent SERS sensitivity for negatively charged targets on the positively charged SERS substrate. Both experimental and theoretical studies confirm that the SERS sensitivity is determined by the electrostatic interaction between the target and linker. This interaction is not only manipulated by the protonation capacity of the linker and its surface adsorption configuration and geometry but also significantly determined by the target's structure, encompassing electronegativity and the number of interaction sites. The optimized interaction leads to a marked improvement in detection sensitivity of up to 1−3 orders of magnitude. The interaction mechanism revealed in this work not only provides theoretical guidance and technical support for electrostatically driven SERS detection but also offers a conceptual framework that can be extended to various SERS detections based on diverse surface forces.
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