Direct Observation of Polaritonic Chemistry by Nuclear Magnetic Resonance Spectroscopy.

Polaritonic chemistry is emerging as a powerful approach to modifying the properties and reactivity of molecules and materials. However, probing how the electronics and dynamics of molecular systems change under strong coupling has been challenging due to the narrow range of spectroscopic techniques that can be applied in situ. Here we develop microfluidic optical cavities for vibrational strong coupling (VSC) that are compatible with nuclear magnetic resonance (NMR) spectroscopy using standard liquid NMR tubes.

Submolecular-scale control of phototautomerization.

Optically activated reactions initiate biological processes such as photosynthesis or vision, but can also control polymerization, catalysis or energy conversion. Methods relying on the manipulation of light at macroscopic and mesoscopic scales are used to control on-surface photochemistry, but do not offer atomic-scale control. Here we take advantage of the confinement of the electromagnetic field at the apex of a scanning tunnelling microscope tip to drive the phototautomerization of a free-base phthalocyanine with submolecular precision.

Solvent Polarity under Vibrational Strong Coupling.

Vibrational strong coupling (VSC) occurs when molecular vibrations hybridize with the modes of an optical cavity, an interaction mediated by vacuum fluctuations. VSC has been shown to influence the rates and selectivity of chemical reactions. However, a clear understanding of the mechanism at play remains elusive.

Correction: Environmentally responsive hydrogel composites for dynamic body thermoregulation.

Correction for 'Environmentally responsive hydrogel composites for dynamic body thermoregulation' by M. Garzón Altamirano , , 2023, , 2360-2369, https://doi.org/10.

Environmentally responsive hydrogel composites for dynamic body thermoregulation.

Hydrogel composites exhibiting dynamic thermo-hydro responsive modulation of infrared radiation (IR) in the 5-15 μm range are designed for personalized body thermoregulation. Fabrication of the proposed system relies on the periodic arrangement of submicron-sized spherical fine silica (SiO) particles within poly(-isopropylacrylamide) (PNIPAM)-based hydrogels. The dependence of the SiO particles content on the IR reflection, followed by its modulation in response to any immediate environmental changes are thereby investigated.

Melt Spinning of Flexible and Conductive Immiscible Thermoplastic/Elastomer Monofilament for Water Detection.

In many textile fields, such as industrial structures or clothes, one way to detect a specific liquid leak is the electrical conductivity variation of a yarn. This yarn can be developed using melt spun of Conductive Polymer Composites (CPCs), which blend insulating polymer and electrically conductive fillers. This study examines the influence of the proportions of an immiscible thermoplastic/elastomer blend for its implementation and its water detection.

Supramolecular Assembly of Conjugated Polymers under Vibrational Strong Coupling.

Strong coupling plays a significant role in influencing chemical reactions and tuning material properties by modifying the energy landscapes of the systems. Here we study the effect of vibrational strong coupling (VSC) on supramolecular organization. For this purpose, a rigid-rod conjugated polymer known to form gels was strongly coupled together with its solvent in a microfluidic IR Fabry-Perot cavity.

Large Enhancement of Ferromagnetism under a Collective Strong Coupling of YBCO Nanoparticles.

Light-Matter strong coupling in the vacuum limit has been shown, over the past decade, to enhance material properties. Oxide nanoparticles are known to exhibit weak ferromagnetism due to vacancies in the lattice. Here we report the 700-fold enhancement of the ferromagnetism of YBaCuO nanoparticles under a cooperative strong coupling at room temperature.

Study of the Influence of PCL on the In Vitro Degradation of Extruded PLA Monofilaments and Melt-Spun Filaments.

This work presents the effect of a melt-spinning process on the degradation behavior of bioresorbable and immiscible poly(d,l-lactide) (PLA) and polycaprolactone (PCL) polymer blends. A large range of these blends, from PLAPCL (90 wt% PLA and 10 wt% PCL) to PLAPCL in increments of 10%, was processed via extrusion (diameter monofilament: ∅ ≈ 1 mm) and melt spinning (80 filaments: 50 to 70 µm each) to evaluate the impact of the PCL ratio and then melt spinning on the hydrolytic degradation of PLA, which allowed for highlighting the potential of a textile-based scaffold in bioresorbable implants. The morphologies of the structures were investigated via extracting PCL with acetic acid and scanning electron microscopy observations.

In Situ Detection of Water Leakage for Textile-Reinforced Composites.

By incorporating electrically conductive yarns into a waterproof membrane, one can detect epoxy resin cracking or liquid leakage. Therefore, this study examined the electrical conductivity variations of several yarns (metallic or carbon-based) for cracking and water detection. The first observations concerned the detectors' feasibility by investigating their conductivity variations during both their resin implementation processes and their resin cracking.

Conductivity and Photoconductivity of a p-Type Organic Semiconductor under Ultrastrong Coupling.

During the past decade, it has been shown that light-matter strong coupling of materials can lead to modified and often improved properties which has stimulated considerable interest. While charge transport can be enhanced in n-type organic semiconductors by coupling the electronic transition and thereby splitting the conduction band into polaritonic states, it is not clear whether the same process can also influence carrier transport in the valence band of p-type semiconductors. Here we demonstrate that it is indeed possible to enhance both the conductivity and photoconductivity of a p-type semiconductor rr-P3HT that is ultrastrongly coupled to plasmonic modes.

Surface-enhanced resonance Raman spectroscopy of heme proteins on a gold grid electrode.

The combination of surface-enhanced resonance Raman spectroscopy (SERRS) and electrochemistry is an ideal tool to study the redox process of the heme proteins and is often performed on silver electrodes. In this manuscript, we present an approach using a microstructured gold surface that serves as the electrochemical working electrode, and at the same time, acts as SERS active substrate. The cell requires a micromolar concentration of sample at the electrode surface.

Selection of Immiscible Polymer Blends Filled with Carbon Nanotubes for Heating Applications.

In many application fields, such as medicine or sports, heating textiles use electrically conductive multifilaments. This multifilament can be developed from conductive polymer composites (CPC), which are blends of an insulating polymer filled with electrically conductive particles. However, this multifilament must have filler content above the percolation threshold, which leads to an increase of the viscosity and problems during the melt spinning process.

Modification of Enzyme Activity by Vibrational Strong Coupling of Water.

Vibrational strong coupling (VSC) has recently emerged as a completely new tool for influencing chemical reactivity. It harnesses electromagnetic vacuum fluctuations through the creation of hybrid states of light and matter, called polaritonic states, in an optical cavity resonant to a molecular absorption band. Here, we investigate the effect of vibrational strong coupling of water on the enzymatic activity of pepsin, where a water molecule is directly involved in the enzyme's chemical mechanism.

Microstructure Evolution of Immiscible PP-PVA Blends Tuned by Polymer Ratio and Silica Nanoparticles.

Composites of polypropylene (PP) and water soluble poly(vinyl alcohol) (PVA) can become an environmentally friendly precursor in preparing porous material, and their biphasic morphology needs to be manipulated. In this work, PP-PVA extrudates were prepared with a twin-screw extruder, and different PP/PVA ratios were employed to manipulate the morphology of the blends. Afterwards, different silicas were imbedded within the blends to further regulate the biphasic microstructure.

Tilting a ground-state reactivity landscape by vibrational strong coupling.

Many chemical methods have been developed to favor a particular product in transformations of compounds that have two or more reactive sites. We explored a different approach to site selectivity using vibrational strong coupling (VSC) between a reactant and the vacuum field of a microfluidic optical cavity. Specifically, we studied the reactivity of a compound bearing two possible silyl bond cleavage sites-Si-C and Si-O, respectively-as a function of VSC of three distinct vibrational modes in the dark.

Current crowding issues on nanoscale planar organic transistors for spintronic applications.

The predominance of interface resistance makes current crowding ubiquitous in short channel organic electronics devices but its impact on spin transport has never been considered. We investigate electrochemically doped nanoscale PBTTT short channel devices and observe the smallest reported values of crowding lengths, found for sub-100 nm electrodes separation. These observed values are nevertheless exceeding the spin diffusion lengths reported in the literature.

Anti-coalescence of bosons on a lossy beam splitter.

Two-boson interference, a fundamentally quantum effect, has been extensively studied with photons through the Hong-Ou-Mandel effect and observed with guided plasmons. Using two freely propagating surface plasmon polaritons (SPPs) interfering on a lossy beam splitter, we show that the presence of loss enables us to modify the reflection and transmission factors of the beam splitter, thus revealing quantum interference paths that do not exist in a lossless configuration. We investigate the two-plasmon interference on beam splitters with different sets of reflection and transmission factors.

Multiple Rabi Splittings under Ultrastrong Vibrational Coupling.

From the high vibrational dipolar strength offered by molecular liquids, we demonstrate that a molecular vibration can be ultrastrongly coupled to multiple IR cavity modes, with Rabi splittings reaching 24% of the vibration frequencies. As a proof of the ultrastrong coupling regime, our experimental data unambiguously reveal the contributions to the polaritonic dynamics coming from the antiresonant terms in the interaction energy and from the dipolar self-energy of the molecular vibrations themselves. In particular, we measure the opening of a genuine vibrational polaritonic band gap of ca.

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.

Application of Flame-Retardant Double-Layered Shell Microcapsules to Nonwoven Polyester.

A microencapsulated flame retardant was used in order to produce a flame retardant nonwoven substrate. Melamine-formaldehyde polymer-shell microcapsules, containing Afflamit PLF 280 (resorcinol bis(diphenyl phosphate)) as the core substance, were coated by an outer thermoplastic wall (polystyrene (PS) or poly(methyl methacrylate)), before being applied to a core/sheet-type bi-component PET/co-PET spunbond nonwoven substrate using impregnation. The outer wall of the microcapsules was heated to the softening temperature of the thermoplastic shell in order to be bonded onto the textile fibres.

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.