Surface‐enhanced Raman spectroscopy (SERS) is now widely used as a rapid and inexpensive tool for chemical/biochemical analysis. The method can give enormous increases in the intensities of the Raman signals of low‐concentration molecular targets if they are adsorbed on suitable enhancing substrates, which are typically composed of nanostructured Ag or Au. However, the features of SERS that allow it to be used as a chemical sensor also mean that it can be used as a powerful probe of the surface chemistry of any nanostructured material that can provide SERS enhancement. This is important because it is the surface chemistry that controls how these materials interact with their local environment and, in real applications, this interaction can be more important than more commonly measured properties such as morphology or plasmonic absorption. Here, the opportunity that this approach to SERS provides is illustrated with examples where the surface chemistry is both characterized and controlled in order to create functional nanomaterials.

SummaryRadical-based carbonylation reactions of alkyl halides were conducted in a microflow reactor under pressurized carbon monoxide gas. Good to excellent yields of carbonylated products were obtained via radical formylation, carbonylative cyclization and three-component coupling reactions, using tributyltin hydride or TTMSS as a radical mediator.

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Inspired by the enchanting bioluminescence of fireflies, herein microfluidic droplet‐based ‘fireflies’ for non‐invasive biphasic chemical analysis are demonstrated. Bicompartmental droplets are created where a model analyte is transported from the aqueous compartment to the adjacent ionic liquid segment, yielding a bright fluid firefly structure via a localized catalytic reaction. Analysis of fluorescence emission kinetics and a method to passively decouple the two compartments at a constriction are presented.