Molecular Chemistry in Cavity Strong Coupling.

The coherent exchange of energy between materials and optical fields leads to strong light-matter interactions and so-called polaritonic states with intriguing properties, halfway between light and matter. Two decades ago, research on these strong light-matter interactions, using optical cavity (vacuum) fields, remained for the most part the province of the physicist, with a focus on inorganic materials requiring cryogenic temperatures and carefully fabricated, high-quality optical cavities for their study. This review explores the history and recent acceleration of interest in the application of polaritonic states to molecular properties and processes. The enormous collective oscillator strength of dense films of organic molecules, aggregates, and materials allows cavity vacuum field strong coupling to be achieved at room temperature, even in rapidly fabricated, highly lossy metallic optical cavities. This has put polaritonic states and their associated coherent phenomena at the fingertips of laboratory chemists, materials scientists, and even biochemists as a potentially new tool to control molecular chemistry. The exciting phenomena that have emerged suggest that polaritonic states are of genuine relevance within the molecular and material energy landscape.

Autotuning of Vibrational Strong Coupling for Site-Selective Reactions.

Site-selective chemistry opens new paths for the synthesis of technologically important molecules. When a reactant is placed inside a Fabry-Perot (FP) cavity, energy exchange between molecular vibrations and resonant cavity photons results in vibrational strong coupling (VSC). VSC has recently been implicated in modified chemical reactivity at specific reactive sites. However, as a reaction proceeds inside an FP cavity, the refractive index of the reaction solution changes, detuning the cavity mode away from the vibrational mode and weakening the VSC effect. Here we overcome this issue, developing actuatable FP cavities to allow automated tuning of cavity mode energy to maintain maximized VSC during a reaction. As an example, the site-selective reaction of the aldehyde over the ketone in 4-acetylbenzaldehyde is achieved by automated cavity tuning to maintain optimal VSC of the ketone carbonyl stretch during the reaction. A nearly 50 % improvement in site-selective reactivity is observed compared to an FP cavity with static mirrors, demonstrating the utility of actuatable FP cavities as microreactors for organic chemistry.

Lithography-free synthesis of periodic, vertically-aligned, multi-walled carbon nanotube arrays.

Until now, the growth of periodic vertically aligned multi-walled carbon nanotube (VA-MWCNT) arrays was dependent on at least one lithography step during fabrication. Here, we demonstrate a lithography-free fabrication method to grow hexagonal arrays of self-standing VA-MWCNTs with tunable pitch and MWCNT size. The MWCNTs are synthesized by plasma enhanced chemical vapor deposition (PECVD) from Ni catalyst particles. Template guided dewetting of a thin Ni film on a hexagonally close-packed silica particle monolayer provides periodically distributed Ni catalyst particles as seeds for the growth of the periodic MWCNT arrays. The diameter of the silica particles directly controls the pitch of the periodic VA-MWCNT arrays from 600 nm to as small as 160 nm. The diameter and length of the individual MWCNTs can also be readily adjusted and are a function of the Ni particle size and PECVD time. This unique method of lithography-free growth of periodic VA-MWCNT arrays can be utilized for the fabrication of large-scale biomimetic materials.

Modulation of Prins Cyclization by Vibrational Strong Coupling.

Light-molecule strong coupling has emerged within the last decade as a new method to control chemical reactions. A few years ago it was discovered that chemical reactivity could be altered by vibrational strong coupling (VSC). Only a limited number of reactions have been investigated under VSC to date, including solvolysis and deprotection reactions. Here the effect of VSC on a series of aldehydes and ketones undergoing Prins cyclization, an important synthetic step in pharmaceutical chemistry, is investigated. A decrease of the second-order rate constant with VSC of the reactant carbonyl stretching groups is observed. We also observe an increased activation energy due to VSC, but proportional changes in activation enthalpy and entropy, suggesting no substantive change in reaction pathway. The addition of common cycloaddition reactions to the stable of VSC-modified chemical reactions is another step towards establishing VSC as a genuine tool for synthetic chemistry.

Frequency Shift Raman-Based Sensing of Serum MicroRNAs for Early Diagnosis and Discrimination of Primary Liver Cancers.

Frequency shift surface-enhanced Raman scattering (SERS) achieves multiplex microRNA sensing for early serological diagnosis of, and discrimination between, primary liver cancers in a patient cohort for whom only biopsy is effective clinically. Raman reporters microprinted on plasmonic substrates shift their vibrational frequencies upon biomarker binding with a dynamic range allowing direct, multiplex assay of serum microRNAs and the current best protein biomarker, α-fetoprotein. Benchmarking against current gold-standard polymerase chain reaction and chemiluminescence methods validates the assay. The work further establishes the frequency shift approach, sensing shifts in an intense SERS band, as a viable alternative to conventional SERS sensing which involves the more difficult task of resolving a peak above noise at ultralow analyte concentrations.

Voltage-Controlled Switching of Strong Light-Matter Interactions using Liquid Crystals.

We experimentally demonstrate a fine control over the coupling strength of vibrational light-matter hybrid states by controlling the orientation of a nematic liquid crystal. Through an external voltage, the liquid crystal is seamlessly switched between two orthogonal directions. Using these features, for the first time, we demonstrate electrical switching and increased Rabi splitting through transition dipole moment alignment. The C-Nstr vibration on the liquid crystal molecule is coupled to a cavity mode, and FT-IR is used to probe the formed vibropolaritonic states. A switching ratio of the Rabi splitting of 1.78 is demonstrated between the parallel and the perpendicular orientation. Furthermore, the orientational order increases the Rabi splitting by 41 % as compared to an isotropic liquid. Finally, by examining the influence of molecular alignment on the Rabi splitting, the scalar product used in theoretical modeling between light and matter in the strong coupling regime is verified.

Coherent Coupling of WS2 Monolayers with Metallic Photonic Nanostructures at Room Temperature.

Room temperature strong coupling of WS2 monolayer exciton transitions to metallic Fabry-Pérot and plasmonic optical cavities is demonstrated. A Rabi splitting of 101 meV is observed for the Fabry-Pérot cavity. The enhanced magnitude and visibility of WS2 monolayer strong coupling is attributed to the larger absorption coefficient, the narrower line width of the A exciton transition, and greater spin-orbit coupling. For WS2 coupled to plasmonic arrays, the Rabi splitting still reaches 60 meV despite the less favorable coupling conditions, and displays interesting photoluminescence features. The unambiguous signature of WS2 monolayer strong coupling in easily fabricated metallic resonators at room temperature suggests many possibilities for combining light-matter hybridization with spin and valleytronics.

High-Efficiency Second-Harmonic Generation from Hybrid Light-Matter States.

We report a novel approach to modify the second order nonlinear optical (NLO) susceptibility of organic nanofiber crystals by hybridization with the optical modes of microcavities in the strong coupling regime. The wavelength dependence of the SHG efficiency displays two intense peaks corresponding to the so-formed light-matter hybrid states. Our results demonstrate an enhancement of the resonant SHG efficiency of the lower polariton by 2 orders of magnitude for the collectively coupled molecules as compared to that of the same material outside the microcavity. This study is a proof of principle that opens a new direction for NLO of organic materials in subwavelength resonators.

Energy Transfer between Spatially Separated Entangled Molecules.

Light-matter strong coupling allows for the possibility of entangling the wave functions of different molecules through the light field. We hereby present direct evidence of non-radiative energy transfer well beyond the Förster limit for spatially separated donor and acceptor cyanine dyes strongly coupled to a cavity. The transient dynamics and the static spectra show an energy transfer efficiency approaching 37 % for donor-acceptor distances ≥100 nm. In such systems, the energy transfer process becomes independent of distance as long as the coupling strength is maintained. This is consistent with the entangled and delocalized nature of the polaritonic states.

Non-Radiative Energy Transfer Mediated by Hybrid Light-Matter States.

We present direct evidence of enhanced non-radiative energy transfer between two J-aggregated cyanine dyes strongly coupled to the vacuum field of a cavity. Excitation spectroscopy and femtosecond pump-probe measurements show that the energy transfer is highly efficient when both the donor and acceptor form light-matter hybrid states with the vacuum field. The rate of energy transfer is increased by a factor of seven under those conditions as compared to the normal situation outside the cavity, with a corresponding effect on the energy transfer efficiency. The delocalized hybrid states connect the donor and acceptor molecules and clearly play the role of a bridge to enhance the rate of energy transfer. This finding has fundamental implications for coherent energy transport and light-energy harvesting.

Ground-State Chemical Reactivity under Vibrational Coupling to the Vacuum Electromagnetic Field.

The ground-state deprotection of a simple alkynylsilane is studied under vibrational strong coupling to the zero-point fluctuations, or vacuum electromagnetic field, of a resonant IR microfluidic cavity. The reaction rate decreased by a factor of up to 5.5 when the Si-C vibrational stretching modes of the reactant were strongly coupled. The relative change in the reaction rate under strong coupling depends on the Rabi splitting energy. Product analysis by GC-MS confirmed the kinetic results. Temperature dependence shows that the activation enthalpy and entropy change significantly, suggesting that the transition state is modified from an associative to a dissociative type. These findings show that vibrational strong coupling provides a powerful approach for modifying and controlling chemical landscapes and for understanding reaction mechanisms.

Enhanced Raman Scattering from Vibro-Polariton Hybrid States.

Ground-state molecular vibrations can be hybridized through strong coupling with the vacuum field of a cavity optical mode in the infrared region, leading to the formation of two new coherent vibro-polariton states. The spontaneous Raman scattering from such hybridized light-matter states was studied, showing that the collective Rabi splitting occurs at the level of a single selected bond. Moreover, the coherent nature of the vibro-polariton states boosts the Raman scattering cross-section by two to three orders of magnitude, revealing a new enhancement mechanism as a result of vibrational strong coupling. This observation has fundamental consequences for the understanding of light-molecule strong coupling and for molecular science.

Membrane remodeling processes induced by phospholipase action.

Important cellular events such as division require drastic changes in the shape of the membrane. These remodeling processes can be triggered by the binding of specific proteins or by changes in membrane composition and are linked to phospholipid metabolism for which dedicated enzymes, named phospholipases, are responsible. Here wide-field fluorescence microscopy is used to visualize shape changes induced by the action of phospholipase A1 on dye-labeled supported membranes of POPC (1-palmitoyl-2-oleoly-sn-glycero-3-phosphocholine). Time-lapse imaging demonstrates that layers either shrink and disappear or fold and collapse into vesicles. These vesicles can undergo further transformations such as budding, tubulation, and pearling within 5 min of formation. Using dye-labeled phospholipases, we can monitor the presence of the enzyme at specific positions on the membrane as the shape transformations occur. Furthermore, incorporating the products of hydrolysis into POPC membranes is shown to induce transformations similar to those observed for enzyme action. The results suggest that phospholipase-mediated hydrolysis plays an important role in membrane transformations by altering the membrane composition, and a model is proposed for membrane curvature based on the presence and shape of hydrolysis products.

Photofunctional nanomodulators for bioexcitation.

A single organism comprises diverse types of cells. To acquire a detailed understanding of the biological functions of each cell, comprehensive control and analysis of homeostatic processes at the single-cell level are required. In this study, we develop a new type of light-driven nanomodulator comprising dye-functionalized carbon nanohorns (CNHs) that generate heat and reactive oxygen species under biologically transparent near-infrared (NIR) laser irradiation. By exploiting the physicochemical properties of the nanohorns, cellular calcium ion flux and membrane currents were successfully controlled at the single-cell level. In addition, the nanomodulator allows a remote bioexcitation of tissues during NIR laser exposure making this system a powerful tool for single-cell analyses and innovative cell therapies.

Strong light-molecule coupling on plasmonic arrays of different symmetry.

The strong coupling of porphyrin J-aggregates to plasmonic nanostructures of different symmetry is investigated. The nanostructures of higher symmetry show the strongest interaction with the molecular layer, suggesting that surface plasmon mode degeneracy plays an important role in the coupling efficiency. At high coupling strengths a new, weakly dispersive mode appears which has recently been predicted theoretically to be due to long-range energy transfer between molecules mediated by surface plasmons. These findings point to new ways for optimizing strong coupling and thereby realize its full potential for molecular and material science.

Polariton dynamics under strong light-molecule coupling.

We present a comprehensive experimental study of the photophysical properties of a molecule-cavity system under strong coupling conditions, using steady-state and femtosecond time-resolved emission and absorption techniques to selectively excite the lower and upper polaritons as well as the reservoir of uncoupled molecules. Our results demonstrate the complex decay routes in such hybrid systems and that, contrary to expectations, the lower polariton is intrinsically long-lived.

Thermodynamics of molecules strongly coupled to the vacuum field.

The thermodynamics of strong coupling between molecules and the vacuum field is analyzed and the Gibbs free energy, the enthalpy, and entropy of the coupling process are determined for the first time. The thermodynamic parameters are a function of the Rabi splitting and the microscopic solvation. The results provide a new framework for understanding light-molecule strong coupling.

Spectroelectrochemistry of CdSe/CdxZn1-xS Nanoplatelets.

We report an unexpected enhancement of photoluminescence (PL) in CdSe-based core/shell nanoplatelets (NPLs) upon electrochemical hole injection. Moderate hole doping densities induce an enhancement of more than 50% in PL intensity. This is accompanied by a narrowing and blue-shift of the PL spectrum. Simultaneous, time-resolved PL experiments reveal a slower luminescence decay. Such hole-induced PL brightening in NPLs is in stark contrast to the usual observation of PL quenching of CdSe-based quantum dots following hole injection. We propose that hole injection removes surface traps responsible for the formation of negative trions, thereby blocking nonradiative Auger processes. Continuous photoexcitation causes the enhanced PL intensity to decrease back to its initial level, indicating that photocharging is a key step leading to loss of PL luminescence during normal aging. Modulating the potential can be used to reversibly enhance or quench the PL, which enables electro-optical switching.

A Shear-Thinning, Self-Healing, Dual-Cross Linked Hydrogel Based on Gelatin/Vanillin/Fe3+ /AGP-AgNPs: Synthesis, Antibacterial, and Wound-Healing Assessment.

A shear-thinning and self-healing hydrogel based on a gelatin biopolymer is synthesized using vanillin and Fe3+ as dual crosslinking agents. Rheological studies indicate the formation of a strong gel found to be injectable and exhibit rapid self-healing (within 10 min). The hydrogels also exhibited a high degree of swelling, suggesting potential as wound dressings since the absorption of large amounts of wound exudate, and optimum moisture levels, lead to accelerated wound healing. Andrographolide, an anti-inflammatory natural product is used to fabricate silver nanoparticles, which are characterized and composited with the fabricated hydrogels to imbue them with anti-microbial activity. The nanoparticle/hydrogel composites exhibit activity against Escherichia coli, Staphylococcus aureus, and Burkholderia pseudomallei, the pathogen that causes melioidosis, a serious but neglected disease affecting southeast Asia and northern Australia. Finally, the nanoparticle/hydrogel composites are shown to enhance wound closure in animal models compared to the hydrogel alone, confirming that these hydrogel composites hold great potential in the biomedical field.

Selective crystallization via vibrational strong coupling.

The coupling of (photo)chemical processes to optical cavity vacuum fields is an emerging method for modulating molecular and material properties. Recent reports have shown that strong coupling of the vibrational modes of solvents to cavity vacuum fields can influence the chemical reaction kinetics of dissolved solutes. This suggests that vibrational strong coupling might also effect other important solution-based processes, such as crystallization from solution. Here we test this hitherto unexplored notion, investigating pseudopolymorphism in the crystallization from water of ZIF metal-organic frameworks inside optical microcavities. We find that ZIF-8 crystals are selectively obtained from solution inside optical microcavities, where the OH stretching vibration of water is strongly coupled to cavity vacuum fields, whereas mixtures of ZIF-8 and ZIF-L are obtained otherwise. Moreover, ZIF crystallization is accelerated by solvent vibrational strong coupling. This work suggests that cavity vacuum fields might become a tool for materials synthesis, biasing molecular self-assembly and driving macroscopic material outcomes.