Highly contrast epi‐surface‐enhanced coherent anti‐Stokes Raman scattering (SECARS) microimages of Au‐nanoparticle‐bound organic reporter molecule distributions at a surface of novel surface‐enhanced Raman scattering (SERS)‐active metamaterial junctions, based on nanoparticles spread over a nanostructured CeO2 faceted dielectric film, deposited on an Al sublayer, were recorded at two‐color picosecond excitation of the surface in the near‐infrared spectral range. For this, a scanning confocal laser‐based micro‐CARS spectrometer was employed. The investigations showed that at Raman resonant laser excitation of the molecules/Au‐NP conjugates immobilized on the surface strong SECARS signals can be generated with laser powers not deteriorating the conjugates. Coupling CARS with the plasmonic metamaterial structures under investigation provided excellent chemical imaging contrast (up to 400) for biochemically relevant 5‐thio(2‐nitrobenzoic acid) and 4‐mercaptophenylboronic acid reporter molecules. Taking into account easy handling and utmost long‐term stability of the investigated metamaterial junction at ambient conditions, it might be considered as a promising perspective for a single‐molecule‐sensitivity surface‐enhanced Raman scattering or SECARS biosensor.
This paper presents a cost-effective approach for the template-assisted electrodeposition fabrication of substrates for surface-enhanced Raman scattering (SERS) with metal nanowires (NWs) grown in pores of polymer track-etched membranes (TM). This technique allows the synthesis of NWs array with its certain surface density and diameter (from dozen to hundreds of nm). NWs length also may be varied (order of μm) by controlling deposition time. Here we grow vertical Ag-NWs which are leaning towards their nearest neighbors, forming self-assembled bundles whose parameters depend on the NW aspect ratio (length to diameter). We show that in such bundles there are “hot spots” in the nm-gaps between NWs tips. Computer simulations have demonstrated a strong enhancement of the electric field within these hot spots; thus, the Raman signal is markedly amplified for analyte molecules placed directly inside the gaps. We have experimentally proved the potential of this SERS-technique on the example of 4-Mercaptophenylboronic acid (4-MPBA). For 4-MPBA the maximal enhancement of Raman signal was found at NWs length of ~1.6 μm and diameter of ~100 nm. The effect is higher (up to twice) if “wet” substrate is used just immediately after the TM polymer removal so that the tips are brought to lean after analyte exposure. We suggest this new type of nanostructured SERS-substrates as a base of effective sensing of extremely low concentration of analytes.
Angiotensin I‐converting enzyme (ACE) is a glycoprotein, consisting of two homologous domains within a single polypeptide chain. ACE concentration in biological fluids is an important parameter of clinical observation; its increase or decrease may accompany various pathologies. Currently, the exact crystal structure of the two‐domain ACE form is still unknown because of microheterogeneity and intensity of the enzyme glycosylation. Raman spectroscopy provides the qualitative and quantitative analysis of many compounds, including proteins. For the first time, surface‐enhanced Raman scattering (SERS) spectra of native and thermo‐denatured human ACE have been demonstrated with full assignment. Denaturation leads to SERS intensity increase and bands shifting. Detailed band assignment and discussion are included to elucidate the potential site of ACE interaction with the silver surface. Based on SERS spectra, we characterized the region on the ACE molecule in contact with the substrate and demonstrated the model of the two‐domain ACE adsorbed on a silver matrix.
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