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Surface-enhanced Raman spectroscopy (SERS) has great potential as an analytical technique for environmental analyses. In this study, we fabricated highly porous gold (Au) supraparticles ( i.e. , ∼100 μm diameter agglomerates of primary nano-sized particles) and evaluated their applicability as SERS substrates for the sensitive detection of environmental contaminants. Facile supraparticle fabrication was achieved by evaporating a droplet containing an Au and polystyrene (PS) nanoparticle mixture on a superamphiphobic nanofilament substrate. Porous Au supraparticles were obtained through the removal of the PS phase by calcination at 500 °C. The porosity of the Au supraparticles was readily adjusted by varying the volumetric ratios of Au and PS nanoparticles. Six environmental contaminants (malachite green isothiocyanate, rhodamine B, benzenethiol, atrazine, adenine, and gene segment) were successfully adsorbed to the porous Au supraparticles, and their distinct SERS spectra were obtained. The observed linear dependence of the characteristic Raman peak intensity for each environmental contaminant on its aqueous concentration reveals the quantitative SERS detection capability by porous Au supraparticles. The limit of detection (LOD) for the six environmental contaminants ranged from ∼10 nM to ∼10 μM, which depends on analyte affinity to the porous Au supraparticles and analyte intrinsic Raman cross-sections. The porous Au supraparticles enabled multiplex SERS detection and maintained comparable SERS detection sensitivity in wastewater influent. Overall, we envision that the Au supraparticles can potentially serve as practical and sensitive SERS devices for environmental analysis applications. 

Multicellular systems, such as microbial biofilms and cancerous tumors, feature complex biological activities coordinated by cellular interactions mediated via different signaling and regulatory pathways, which are intrinsically heterogeneous, dynamic, and adaptive. However, due to their invasiveness or their inability to interface with native cellular networks, standard bioanalysis methods do not allow in situ spatiotemporal biochemical monitoring of multicellular systems to capture holistic spatiotemporal pictures of systems‐level biology. Here, a high‐throughput reverse nanoimprint lithography approach is reported to create biomimetic transparent nanoplasmonic microporous mesh (BTNMM) devices with ultrathin flexible microporous structures for spatiotemporal multimodal surface‐enhanced Raman spectroscopy (SERS) measurements at the bio‐interface. It is demonstrated that BTNMMs, supporting uniform and ultrasensitive SERS hotspots, can simultaneously enable spatiotemporal multimodal SERS measurements for targeted pH sensing and non‐targeted molecular detection to resolve the diffusion dynamics for pH, adenine, and Rhodamine 6G molecules in agarose gel. Moreover, it is demonstrated that BTNMMs can act as multifunctional bio‐interfaced SERS sensors to conduct in situ spatiotemporal pH mapping and molecular profiling ofEscherichia colibiofilms. It is envisioned that the ultrasensitive multimodal SERS capability, transport permeability, and biomechanical compatibility of the BTNMMs can open exciting avenues for bio‐interfaced multifunctional sensing applications both in vitro and in vivo.

 

Surface‐enhanced Raman spectroscopy (SERS) has become a sensitive detection technique for biochemical analysis. Despite significant research efforts, most SERS substrates consisting of single‐resonant plasmonic nanostructures on the planar surface suffer from limitations of narrowband SERS operation and unoptimized nano‐bio interface with living cells. Here, it is reported that nanolaminate plasmonic nanocavities on 3D vertical nanopillar arrays can support a broadband SERS operation with large enhancement factors (>10⁶) under laser excitations at 532, 633, and 785 nm. The multi‐band Raman mapping measurements show that nanolaminate plasmonic nanocavities on vertical nanopillar arrays exhibit broadband uniform SERS performance with diffraction‐limited resolution at a single nanopillar footprint. By selective exposure of embedded plasmonic hotspots in individual metal–insulator–metal (MIM) nanogaps, nanoscale broadband SERS operation at the single MIM nanocavity level with visible and near‐infrared (vis–NIR) excitations is demonstrated. Numerical studies reveal that nanolaminate plasmonic nanocavities on vertical nanopillars can support multiple hybridized plasmonic modes to concentrate optical fields across a broadband wavelength range from 500 to 900 nm at the nanoscale.