Plasmonic Au@Ag@mSiO2 Nanorattles for In Situ Imaging of Bacterial Metabolism by Surface-Enhanced Raman Scattering Spectroscopy.

It is well known that microbial populations and their interactions are largely influenced by their secreted metabolites. Noninvasive and spatiotemporal monitoring and imaging of such extracellular metabolic byproducts can be correlated with biological phenotypes of interest and provide new insights into the structure and development of microbial communities. Herein, we report a surface-enhanced Raman scattering (SERS) hybrid substrate consisting of plasmonic Au@Ag@mSiO2 nanorattles for optophysiological monitoring of extracellular metabolism in microbial populations. A key element of the SERS substrate is the mesoporous silica shell encapsulating single plasmonic nanoparticles, which furnishes colloidal stability and molecular sieving capabilities to the engineered nanostructures, thereby realizing robust, sensitive, and reliable measurements. The reported SERS-based approach may be used as a powerful tool for deciphering the role of extracellular metabolites and physicochemical factors in microbial community dynamics and interactions.

Plasmonic MOF Thin Films with Raman Internal Standard for Fast and Ultrasensitive SERS Detection of Chemical Warfare Agents in Ambient Air.

Surface-enhanced Raman scattering (SERS) is a powerful spectroscopic technique for selective detection and quantification of molecules at extremely low concentrations. However, practical SERS applications for gaseous chemicals with small cross section is still in its early stages. We herein report a plasmonic-sorbent thin-film platform with integrated Raman internal standard with outstanding SERS sensing capabilities for chemical warfare agents (CWA) simulants. The thin film is constituted of close-packed core-shell Au@Ag nanorods individually encapsulated within a ZIF-8 framework (Au@Ag@ZIF-8). While the Au@Ag nanoparticles amplify the Raman signal of molecules located near their surface, the ZIF-8 framework plays a key role in the trapping of the dimethyl methylphosphonate (DMMP) or 2-chloroethyl ethyl sulfide (CEES) from the gas phase as well as Raman internal standard. The underlying adsorption mechanism of the molecules within the ZIF-8 framework as well as the interaction between DMMP and Ag surface are investigated by computational simulations. Outstanding SERS sensing capabilities of Au@Ag@ZIF-8 thin films, in terms of response time, quantification limit, reproducibility, and recyclability, are demonstrated for dimethyl methylphosphonate (DMMP) and 2-chloroethyl ethyl sulfide (CEES), selected as CWA simulants of sarin gas and mustard gas, respectively. A limit of detection (LOD) of 0.2 ppbV is reported for DMMP. Additionally, experiments performed with portable Raman equipment detect 2.5 ppmV for DMMP in ambient air and 76 ppbV for CEES in N2, with response times of 21 and 54 s, respectively. This proof of concept opens the door for handheld SERS-based gas sensing at ultralow concentrations in practical applications, such as homeland security, critical infrastructure protection, chemical process monitoring, or personalized medicine.

Pd nanoparticles as a plasmonic material: synthesis, optical properties and applications.

This review provides an overview of current progress in Pd nanoparticles supporting localized surface plasmon resonance and their applications. We begin by analyzing briefly the optical properties of Pd putting particular focus on outlining the origin of its size- and shape-dependent LSPR, high refractive index sensitivity, and high absorption contribution. The differences in the optical behavior with Au and Ag, the primary plasmonic materials, are highlighted. The main strategies to synthesize Pd nanoparticles, pure or hybrid, with well-defined optical properties are then reviewed. In this section, we include only those works that carry out the study of the optical properties of the nanoparticles. The applications of plasmonic Pd nanoparticles are also discussed in detail. This review is concluded with a section devoted to the future perspectives highlighting the most relevant challenges to be addressed to take Pd nanoparticles from the laboratory to real applications.

Encapsulation of Single Plasmonic Nanoparticles within ZIF-8 and SERS Analysis of the MOF Flexibility.

Hybrid nanostructures composed of metal nanoparticles and metal-organic frameworks (MOFs) have recently received increasing attention toward various applications due to the combination of optical and catalytic properties of nanometals with the large internal surface area, tunable crystal porosity and unique chemical properties of MOFs. Encapsulation of metal nanoparticles of well-defined shapes into porous MOFs in a core-shell type configuration can thus lead to enhanced stability and selectivity in applications such as sensing or catalysis. In this study, the encapsulation of single noble metal nanoparticles with arbitrary shapes within zeolitic imidazolate-based metal organic frameworks (ZIF-8) is demonstrated. The synthetic strategy is based on the enhanced interaction between ZIF-8 nanocrystals and metal nanoparticle surfaces covered by quaternary ammonium surfactants. High resolution electron microscopy and tomography confirm a complete core-shell morphology. Such a well-defined morphology allowed us to study the transport of guest molecules through the ZIF-8 porous shell by means of surface-enhanced Raman scattering by the metal cores. The results demonstrate that even molecules larger than the ZIF-8 aperture and pore size may be able to diffuse through the framework and reach the metal core.