Toward Real-Time Monitoring and Control of Single Nanoparticle Properties with a Microbubble Resonator Spectrometer.

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.

Single-particle photothermal imaging via inverted excitation through high-Q all-glass toroidal microresonators.

Whispering-gallery mode (WGM) microresonators have recently been employed as platforms for label-free single-molecule and single-particle detection, imaging, and spectroscopy. However, innovations in device geometry and integration are needed to make WGM microresonators more versatile for biological and chemical applications. Particularly, thick device substrates, originating from wafer-scale fabrication processing, prevent convenient optical interrogation. In this work, we fabricate all-glass toroidal microresonators on a coverslip thickness (~170 µm) substrate, enabling excitation delivery through the sample, simplifying optical integration. Further, we demonstrate the application of this new geometry for single-particle photothermal imaging. Finally, we discover and develop simulations to explain a non-trivial astigmatism in the point spread function (PSF) arising from the curvature of the resonator.

Exploring Electronic Structure and Order in Polymers via Single-Particle Microresonator Spectroscopy.

PEDOT: PSS, a transparent electrically conductive polymer, finds widespread use in electronic devices. While empirical efforts have increased conductivity, a detailed understanding of the coupled electronic and morphological landscapes in PEDOT:PSS has lagged due to substantial structural heterogeneity on multiple length-scales. We use an optical microresonator-based absorption spectrometer to perform single-particle measurements, providing a bottom-up examination of electronic structure and morphology ranging from single PEDOT:PSS polymers to nascent films. Using single-particle spectroscopy with complementary theoretical calculations and ultrafast spectroscopy, we demonstrate that PEDOT:PSS displays bulk-like optical response even in single polymers. We find highly ordered PEDOT assemblies with long-range ordering mediated by the insulating PSS matrix and reveal a preferential surface orientation of PEDOT nanocrystallites absent in bulk films with implications for interfacial electronic communication. Our single-particle perspective provides a unique window into the microscopic structure and electronic properties of PEDOT:PSS.

Sculpting Fano Resonances To Control Photonic-Plasmonic Hybridization.

Hybrid photonic-plasmonic systems have tremendous potential as versatile platforms for the study and control of nanoscale light-matter interactions since their respective components have either high-quality factors or low mode volumes. Individual metallic nanoparticles deposited on optical microresonators provide an excellent example where ultrahigh-quality optical whispering-gallery modes can be combined with nanoscopic plasmonic mode volumes to maximize the system's photonic performance. Such optimization, however, is difficult in practice because of the inability to easily measure and tune critical system parameters. In this Letter, we present a general and practical method to determine the coupling strength and tailor the degree of hybridization in composite optical microresonator-plasmonic nanoparticle systems based on experimentally measured absorption spectra. Specifically, we use thermal annealing to control the detuning between a metal nanoparticle's localized surface plasmon resonance and the whispering-gallery modes of an optical microresonator cavity. We demonstrate the ability to sculpt Fano resonance lineshapes in the absorption spectrum and infer system parameters critical to elucidating the underlying photonic-plasmonic hybridization. We show that including decoherence processes is necessary to capture the evolution of the lineshapes. As a result, thermal annealing allows us to directly tune the degree of hybridization and various hybrid mode quantities such as the quality factor and mode volume and ultimately maximize the Purcell factor to be 104.

Optical Microresonators for Sensing and Transduction: A Materials Perspective.

Optical microresonators confine light to a particular microscale trajectory, are exquisitely sensitive to their microenvironment, and offer convenient readout of their optical properties. Taken together, this is an immensely attractive combination that makes optical microresonators highly effective as sensors and transducers. Meanwhile, advances in material science, fabrication techniques, and photonic sensing strategies endow optical microresonators with new functionalities, unique transduction mechanisms, and in some cases, unparalleled sensitivities. In this progress report, the operating principles of these sensors are reviewed, and different methods of signal transduction are evaluated. Examples are shown of how choice of materials must be suited to the analyte, and how innovations in fabrication and sensing are coupled together in a mutually reinforcing cycle. A tremendously broad range of capabilities of microresonator sensors is described, from electric and magnetic field sensing to mechanical sensing, from single-molecule detection to imaging and spectroscopy, from operation at high vacuum to in live cells. Emerging sensing capabilities are highlighted and put into context in the field. Future directions are imagined, where the diverse capabilities laid out are combined and advances in scalability and integration are implemented, leading to the creation of a sensor unparalleled in sensitivity and information content.

Suppression of Kasha's rule as a mechanism for fluorescent molecular rotors and aggregation-induced emission.

Although there are some proposed explanations for aggregation-induced emission, a phenomenon with applications that range from biosensors to organic light-emitting diodes, current understanding of the quantum-mechanical origin of this photophysical behaviour is limited. To address this issue, we assessed the emission properties of a series of BF2-hydrazone-based dyes as a function of solvent viscosity. These molecules turned out to be highly efficient fluorescent molecular rotors. This property, in addition to them being aggregation-induced emission luminogens, enabled us to probe deeper into their emission mechanism. Time-dependent density functional theory calculations and experimental results showed that the emission is not from the S1 state, as predicted from Kasha's rule, but from a higher energy (>S1) state. Furthermore, we found that suppression of internal conversion to the dark S1 state by restricting the rotor rotation enhances fluorescence, which leads to the proposal that suppression of Kasha's rule is the photophysical mechanism responsible for emission in both viscous solution and the solid state.

Correction: Dynamic ruffling distortion of the heme substrate in non-canonical heme oxygenase enzymes.

Correction for 'Dynamic ruffling distortion of the heme substrate in non-canonical heme oxygenase enzymes' by Amanda B. Graves et al., Dalton Trans., 2016, 45, 10058-10067.

Dynamic ruffling distortion of the heme substrate in non-canonical heme oxygenase enzymes.

Recent work by several groups has established that MhuD, IsdG, and IsdI are non-canonical heme oxygenases that induce significant out-of-plane ruffling distortions of their heme substrates enroute to mycobilin or staphylobilin formation. However, clear explanations for the observations of "nested" S = ½ VTVH MCD saturation magnetization curves at cryogenic temperatures, and exchange broadened (1)H NMR resonances at physiologically-relevant temperatures have remained elusive. Here, MCD and NMR data have been acquired for F23A and F23W MhuD-heme-CN, in addition to MCD data for IsdI-heme-CN, in order to complete assembly of a library of spectroscopic data for cyanide-inhibited ferric heme with a wide range of ruffling deformations. The spectroscopic data were used to evaluate a number of computational models for cyanide-inhibited ferric heme, which ultimately led to the development of an accurate NEVPT2/CASSCF model. The resulting model has a shallow, double-well potential along the porphyrin ruffling coordinate, which provides clear explanations for the unusual MCD and NMR data. The shallow, double-well potential also implies that MhuD-, IsdG-, and IsdI-bound heme is dynamic, and the functional implications of these dynamics are discussed.

Chip-Scale Fabrication of High-Q All-Glass Toroidal Microresonators for Single-Particle Label-Free Imaging.

Whispering-gallery-mode microresonators enable materials for single-molecule label-free detection and imaging because of their high sensitivity to their micro-environment. However, fabrication and materials challenges prevent scalability and limit functionality. All-glass on-chip microresonators significantly reduce these difficulties. Construction of all-glass toroidal microresonators with high quality factor and low mode volume is reported and these are used as platforms for label-free single-particle imaging.