Most bacteria in nature exist as biofilms, which support intercellular signaling processes such as quorum sensing (QS), a cell-to-cell communication mechanism that allows bacteria to monitor and respond to cell density and changes in the environment. Because QS and biofilms are involved in the ability of bacteria to cause disease, there is a need for the development of methods for the non-invasive analysis of QS in natural bacterial populations. Here, by using surface-enhanced resonance Raman scattering spectroscopy, we report rationally designed nanostructured plasmonic substrates for the in-situ, label-free detection of a QS signaling metabolite in growing Pseudomonas aeruginosa biofilms and microcolonies. The in situ, non-invasive plasmonic imaging of QS in biofilms provides a powerful analytical approach for studying intercellular communication on the basis of secreted molecules as signals.

In this minireview, we summarize current research dealing with the combination of noble-metal nanoparticles and different families of supramolecular macrocycles (cyclodextrins, cucurbit[n]urils, calixarenes, and pillar[n]arenes). We intended to select relevant publications on the synthesis of noble-metal nanoparticles with macrocycles acting as capping agents or/and reducing agents, as well as on the post-synthetic metal-nanoparticle modification with macrocycles. We also discuss strategies in which supramolecular chemistry is applied to direct the self-assembly of nanoparticles and formation of polymer composites. We finally describe the main applications of these materials in various fields.

Detection technologies employing optically encoded particles have gained much interest toward clinical diagnostics and drug discovery, but the portfolio of available systems is still limited. The fabrication and characterization of highly stable surface-enhanced resonance Raman scattering (SERRS)-encoded colloids for the identification and imaging of proteins expressed in cells are reported. These plasmonic nanostructures are made of gold octahedra coated with poly(N-isopropylacrylamide) microgels and can be readily encoded with Raman active dyes while retaining high colloidal stability in biofluids. A layer-by-layer polyelectrolyte coating is used to seal the outer surface of the encoded particles and to provide a reactive surface for covalent conjugation with antibodies. The targeted multiplexing capabilities of the SERRS tags are demonstrated by the simultaneous detection and imaging of three tumor-associated surface biomarkers: epidermal growth factor receptor (EGFR), epithelial cell adhesion molecule (EpCAM), and homing cell adhesion molecule (CD44) by SERRS spectroscopy. The plasmonic microgels are able to discriminate tumor A431 (EGFR+/EpCAM+/CD44+) and nontumor 3T3 2.2 (EGFR-/EpCAM-/CD44+) cells while cocultured in vitro.

Palladium nanoparticles (NPs) have received tremendous attention over the years due to their high catalytic activity for various chemical reactions. However, unlike other noble metal nanoparticles such as Au and Ag NPs, they exhibit poor plasmonic properties with broad extinction spectra and less scattering efficiency, and thus limiting their applications in the field of plasmonics. Therefore, it has been challenging to integrate tunable and strong plasmonic properties into catalytic Pd nanoparticles. Here we show that plasmonic Au@Pd nanorods (NRs) with relatively narrow and remarkably tunable optical responses in the NIR region can be obtained by directional growth of Pd on penta-twinned Au NR seeds. We found the presence of bromide ions facilitates the stabilization of facets for the directional growth of Pd shell to obtain Au@Pd nanorods (NR) with controlled length scales. Interestingly, it turns out the Au NR supported Pd NRs exhibit much narrow extinction compared to pure Pd NRs, which makes them suitable for plasmonic sensing applications. Moreover, these nanostructures display, to the best of our knowledge, one of the highest ensemble refractive index sensitivity values reported to date (1067 nm per refractive index unit, RIU). Additionally, we showed the application of such plasmonic Au@Pd NRs for localized surface plasmon resonance (LSPR)-based sensing of hydrogen both in solution as well as on substrate. Finally, we demonstrate the integration of excellent plasmonic properties in catalytic palladium enables the in situ monitoring of a reaction progress by surface-enhanced Raman scattering. We postulate the proposed approach to boost the plasmonic properties of Pd nanoparticles will ignite the design of complex shaped plasmonic Pd NPs to be used in various plasmonic applications such as sensing and in situ monitoring of various chemical reactions.

Microbes produce bioactive chemical compounds to influence the physiology and growth of their neighbors, and our understanding of their biological activities may be enhanced by our ability to visualize such molecules in vivo. We demonstrate here the application of surface-enhanced Raman scattering spectroscopy for simultaneous detection of quorum-sensing-regulated pyocyanin and violacein, produced respectively by Pseudomonas aeruginosa and Chromobacterium violaceum bacterial colonies, grown as a coculture on agar-based plasmonic substrates. Our plasmonic approach allowed us to visualize the expression and spatial distribution of the microbial metabolites in the coculture taking place as a result of interspecies chemical interactions. By combining surface-enhanced Raman scattering spectroscopy with analysis of gene expression we provide insight into the chemical interplay occurring between the interacting bacterial species. This highly sensitive, cost-effective, and easy to implement approach allows spatiotemporal imaging of cellular metabolites in live microbial colonies grown on agar with no need for sample preparation, thereby providing a powerful tool for the analysis of microbial chemotypes.