With the goal of avoiding the need for anhydride additives, the catalytic decarbonylation of p-nitrophenylesters of aliphatic carboxylic acids to their corresponding olefins, including commodity monomers like styrene and acrylates, has been developed. The reaction is catalyzed by palladium complexes in the absence of added ligands and is promoted by alkali/alkaline-earth metal halides. Combination of catalytic decarbonylation and Heck-type coupling with aryl esters in a single pot process demonstrates the viability of employing a carboxylic acid as a "masked olefin" in synthetic processes.

Optical microresonators have widespread application at the frontiers of nanophotonic technology, driven by their ability to confine light to the nanoscale and enhance light–matter interactions. Microresonators form the heart of a recently developed method for single-particle photothermal absorption spectroscopy, whereby the microresonators act as microscale thermometers to detect the heat dissipated by optically pumped, nonluminescent nanoscopic targets. However, translation of this technology to chemically dynamic systems requires a platform that is mechanically stable, solution compatible, and visibly transparent. We report microbubble absorption spectrometers as a versatile platform that meets these requirements. Microbubbles integrate a two-port microfluidic device within a whispering gallery mode microresonator, allowing for the facile exchange of chemical reagents within the resonator’s interior while maintaining a solution-free environment on its exterior. We first leverage these qualities to investigate the photoactivated etching of single gold nanorods by ferric chloride, providing a method for rapid acquisition of spatial and morphological information about nanoparticles as they undergo chemical reactions. We then demonstrate the ability to control nanorod orientation within a microbubble through optically exerted torque, a promising route toward the construction of hybrid photonic-plasmonic systems. Critically, the reported platform advances microresonator spectrometer technology by permitting room-temperature, aqueous experimental conditions, which may be used for time-resolved single-particle experiments on non-emissive, nanoscale analytes engaged in catalytically and biologically relevant chemical dynamics.

The homogeneous dehydrative decarbonylation of fatty acid methyl esters (FAMEs) to form olefins is reported. In order to facilitate cleavage of the unactivated acyl C-O bond of the alkyl ester, a one pot dual-catalytic directing group strategy was developed through optimization of the individual transesterification and decarbonylation reaction steps.

Active control of light–matter interactions using nanophotonic structures is critical for new modalities for solar energy production, cavity quantum electrodynamics (QED), and sensing, particularly at the single-particle level, where it underpins the creation of tunable nanophotonic networks. Coupled plasmonic–photonic systems show great promise toward these goals because of their subwavelength spatial confinement and ultrahigh-quality factors inherited from their respective components. Here, we present a microfluidic approach using microbubble whispering-gallery mode cavities to actively control plasmonic–photonic interactions at the single-particle level. By changing the solvent in the interior of the microbubble, control can be exerted on the interior dielectric constant and, thus, on the spatial overlap between the photonic and plasmonic modes. Qualitative agreement between experiment and simulation reveals the competing roles mode overlap and mode volume play in altering coupling strengths.

<p></p><p></p><p>Optical microresonators have widespread application at the frontiers of nanophotonic technology, driven by their ability to confine light to the nanoscale and enhance light-matter interactions. Microresonators form the heart of a new method for single-particle photothermal absorption spectroscopy, whereby the microresonators act as microscale thermometers to detect the heat dissipated by optically pumped, non-luminescent nanoscopic targets. However, translation of this technology to chemically dynamic systems requires a platform that is mechanically stable, solution compatible, and visibly transparent. We report microbubble absorption spectrometers as a new and versatile platform that meets these requirements. Microbubbles integrate a two-port microfluidic device within a Whispering Gallery Mode (WGM) microresonator, allowing for the facile exchange of chemical reagents within the resonator’s interior while maintaining a solution-free environment on its exterior. We first leverage these qualities to investigate the photo-activated etching of single gold nanorods by ferric chloride, providing a new method for rapid acquisition of spatial and morphological information about nanoparticles as they undergo chemical reactions. We then demonstrate the ability to control nanorod orientation within a microbubble through optically exerted torque, a new route toward the construction of hybrid photonic-plasmonic systems. Critically, the reported platform advances microresonator spectrometer technology by permitting room-temperature, aqueous experimental conditions, opening a regime of time-resolved single-particle experiments on non-emissive, nanoscale analytes engaged in catalytically and biologically relevant chemical dynamics.</p><p></p><p></p>