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. VSC is shown to influence the equilibrium between two conformations of a molecular balance sensitive to London dispersion forces, revealing an apparent change in the equilibrium constant under VSC. In all compounds studied, VSC does not induce detectable changes in chemical shifts, J-couplings, or spin-lattice relaxation times. This unexpected finding indicates that VSC does not substantially affect molecular electron density distributions, and in turn has profound implications for the possible mechanisms at play in polaritonic chemistry under VSC and suggests that the emergence of collective behavior is critical.

Correction: Environmentally responsive hydrogel composites for dynamic body thermoregulation.

Correction for 'Environmentally responsive hydrogel composites for dynamic body thermoregulation' by M. Garzón Altamirano et al., Soft Matter, 2023, 19, 2360-2369, https://doi.org/10.1039/D2SM01548J.

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 (SiO2) particles within poly(N-isopropylacrylamide) (PNIPAM)-based hydrogels. The dependence of the SiO2 particles content on the IR reflection, followed by its modulation in response to any immediate environmental changes are thereby investigated. The addition of 20 wt% of SiO2 allowed the hydrogel composites to reflect 20% of the IR emitted by the human body at constant temperature (i.e. T = 20 °C) and relative humidity (i.e. RH = 0%). According to Bragg's law, we found that the smaller the distance between the SiO2 particles, the higher the IR reflection. The IR reflection further increased to a maximum of 42% when the resulting hydrogel composites are subjected to changes in relative humidity (i.e. RH = 60%) and temperature (i.e. T = 35 °C). Thermography is used to map the IR radiation emitted from the hydrogel composites when placed on the skin of the human body, demonstrating that the composite is actually reflecting IR. The latter results are supported by theoretical models that define the IR reflection profile of the resulting hydrogel composites with respect to the silica content, relative humidity and temperature.

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. The results show that VSC can indeed tilt the reactivity landscape to favor one product over the other. Thermodynamic parameters reveal the presence of a large activation barrier and substantial changes to the activation entropy, confirming the modified chemical landscape under strong coupling.

Conductivity in organic semiconductors hybridized with the vacuum field.

Much effort over the past decades has been focused on improving carrier mobility in organic thin-film transistors by optimizing the organization of the material or the device architecture. Here we take a different path to solving this problem, by injecting carriers into states that are hybridized to the vacuum electromagnetic field. To test this idea, organic semiconductors were strongly coupled to plasmonic modes to form coherent states that can extend over as many as 10(5) molecules and should thereby favour conductivity. Experiments show that indeed the current does increase by an order of magnitude at resonance in the coupled state, reflecting mostly a change in field-effect mobility. A theoretical quantum model confirms the delocalization of the wavefunctions of the hybridized states and its effect on the conductivity. Our findings illustrate the potential of engineering the vacuum electromagnetic environment to modify and to improve properties of materials.

Sorting nanoparticles with intertwined plasmonic and thermo-hydrodynamical forces.

We exploit plasmonic and thermo-hydrodynamical forces to sort gold nanoparticles in a microfluidic environment. In the appropriate regime, the experimental data extracted from a Brownian statistical analysis of the kinetic motions are in good agreement with Mie-type theoretical evaluations of the optical forces acting on the nanoparticles in the plasmonic near field. This analysis enables us to demonstrate the importance of thermal and hydrodynamical effects in a sorting perspective.

Diffraction regimes of single holes.

We investigate both experimentally and theoretically the far-field diffraction patterns of single circular apertures as a function of their diameters d and at a given illumination wavelength λ. We observe the transition between the well-known pseudoscalar regime of large holes (d≫λ) and the less-known vectorial regime of subwavelength ones (d≪λ). Four different diffraction regimes are identified for different d/λ regions, each one with its polarization dependence. A thorough comparison with a theoretical model, which takes into account both finite hole size and the dielectric properties of the metal, allows us to explain and understand the physical processes leading to this behavior. Our results reveal the subtle interplay between two competing factors, one related to polarization symmetries associated with surface-plasmon excitations and the other originating in the coupling of the field to the waveguide mode of the aperture.

Brownian motion in a designer force field: dynamical effects of negative refraction on nanoparticles.

Photonic crystals (PC) have demonstrated unique features that have renewed the fields of classical and quantum optics. Although holding great promises, associated mechanical effects have proven challenging to observe. We demonstrate for the first time that one of the most salient properties of PC, namely negative refraction, can induce specific forces on metal nanoparticles. By integrating a periodically patterned metal film in a fluidic cell, we show that near-field optical forces associated with negatively refracted surface plasmons are capable of controlling particle trajectories. Coupling particle motions to PC band structures draws new approaches and strategies for parallel and high resolution all-optical control of particle flows with applications for micro- and nanofluidic systems.

Self-collimation of surface plasmon beams.

We generate self-collimating surface plasmon beams in a doubly periodic plasmonic grating. The self-collimation effect is understood from the local anisotropy of the isofrequency surface of the grating in the vicinity of the bandgap. The properties of the beams are analyzed by leakage radiation microscopy and show to an unprecedented level significantly reduced diffraction as compared with plasmon beams propagating on a flat metal film.

Plasmonic coherent drive of an optical trap.

We demonstrate that optical trapping can be driven by delocalized surface plasmon modes resonantly excited within a standing wave trap. Dynamical modifications are shown to be determined by the near-field symmetry of the plasmonic modes with negligible thermal effect. With low trapping powers and polarization control, remarkable stiffness enhancements are recorded, the larger the smaller the particle. The results can be simply modeled accounting for a coherent interaction between the plasmon field and the Gaussian standing wave of the trap.

Human immunodeficiency virus-associated thrombotic microangiopathies: clinical characteristics and outcome according to ADAMTS13 activity.

Human immunodeficiency virus (HIV) infection is a risk factor for thrombotic microangiopathy (TMA). We sought whether a severe deficiency in ADAMTS13, the enzyme specifically involved in the cleavage of von Willebrand factor, was associated with specific presenting features and outcome in HIV-associated TMA. In this prospective, multicentre, case-control study, 29 patients of 236 in the French Network on TMA had an HIV-associated TMA. Seventeen patients with severe ADAMTS13 deficiency (ADAMTS13 <5% HIV(+) group) were compared to 12 patients with a detectable ADAMTS13 activity (ADAMTS13 >or=5% HIV(+) group). HIV(+) patients were also compared to 62 patients with idiopathic TMA, either with (45 patients, ADAMTS13 <5% idiopathic group) or without (17 patients, ADAMTS13 >or=5% idiopathic group) severe ADAMTS13 deficiency. ADAMTS13 <5% HIV(+) patients had less AIDS-related complications than ADAMTS13 >or=5% HIV(+) patients (23.5% versus 91.6%, respectively, P = 0.0005) and their median CD4(+) T cell count was higher (P = 0.05). TMA-associated death rate was higher in ADAMTS13 >or=5% HIV(+) patients than in ADAMTS13 <5% HIV(+) patients (50% versus 11.7%, respectively, P = 0.04). In ADAMTS13 <5% patients, TMA-associated death rate was comparable between HIV(+) and idiopathic patients (15.5% in idiopathic patients, P-value was non-significant). By contrast, TMA-associated death rate in ADAMTS13 >or=5% HIV(+) patients was higher than in idiopathic patients (11.7% in idiopathic patients, P = 0.04). In conclusion, HIV-associated TMA with severe ADAMTS13 deficiency have less AIDS-related complications and a higher CD4(+) T cell count. TMA prognosis is better and comparable to this of idiopathic forms.

Optimization of surface plasmons launching from subwavelength hole arrays: modelling and experiments.

The launching of surface plasmons by micro-gratings of subwavelength apertures milled in a thick metal film is important for the development of surface plasmon based circuits. By comparing the near-field optical images of such surface plasmon sources with the results of a Huygens-Fresnel principle based scattering model, we show that the properties of the locally launched SP beams such as divergence or uniformity can be tuned by adjusting the shape of the micro-gratings. This allows us to propose an optimized source array well adapted for providing a narrow, collimated and uniform beam.

Surface plasmon polaritons and their role in the enhanced transmission of light through periodic arrays of subwavelength holes in a metal film.

We present results of the transmitted, reflected, and absorbed power associated with the enhanced transmittance of light through a silver film pierced by a periodic array of subwavelength holes. Comparing experimentally acquired dispersion curves under different polarization conditions shows that the transmission features of the array are consistent with p-polarized resonant modes of the structure. By exploring the regime in which no propagating diffracted orders are allowed, we further show that the transmittance maxima are associated with both reflectance minima and absorption maxima. These new results provide strong experimental evidence for transmission based on diffraction, assisted by the enhanced fields associated with surface plasmon polaritons.

Beaming light from a subwavelength aperture.

Light usually diffracts in all directions when it emerges from a subwavelength aperture, which puts a lower limit on the size of features that can be used in photonics. This limitation can be overcome by creating a periodic texture on the exit side of a single aperture in a metal film. The transmitted light emerges from the aperture as a beam with a small angular divergence (approximately +/-3 degrees ) whose directionality can be controlled. This finding is especially surprising, considering that the radiating region is mainly confined to an area with lateral dimensions comparable to the wavelength of the light. The device occupies no more than one cubic micrometer and, when combined with enhanced transmission, suggests that a wide range of photonic applications is possible.

Direct interpretation of near-field optical images.

The interpretation of the detection process in near-field optical microscopy is reviewed on the basis of a discussion about the possibility of establishing direct comparisons between experimental images and the solutions of Maxwell equations or the electromagnetic local density of states. On the basis of simple physical arguments, it is expected that the solutions of Maxwell equations should agree with images obtained by collecting mode near-field microscopes, while the electromagnetic local density of states should be considered to provide a practical interpretation of illumination mode near-field microscopes. We review collecting mode near-field microscope images where the conditions to obtain good agreement with the solutions of Maxwell equations have indeed been identified. In this context of collecting mode near-field microscopes, a fundamentally different functionality between dielectric and gold-coated tips has been clearly identified experimentally by checking against the solutions of Maxwell equations. It turns out that dielectric tips detect a signal proportional to the optical electric field intensity, whereas gold-coated tips detect a signal proportional to the optical magnetic field intensity. The possible implications of this surprising phenomenon are discussed.

Involvement of p27Kip1 in the G1- and S/G2-phase lengthening mediated by glucocorticoids in normal human lymphocytes.

Glucocorticoids inhibit cell proliferation by inducing cell cycle lengthening. In this report, we have analyzed, in normal peripheral blood lymphocytes, the involvement of p27Kip1 in this slowing of proliferation. Following dexamethasone (DXM) treatment, p27Kip1 expression and regulation varied differently with the level of lymphocyte stimulation. In quiescent cells, DXM inhibited p27Kip1 protein expression by decreasing its rate of synthesis, whereas its half-life and mRNA steady state remained constant. In contrast, in stimulated lymphocytes, DXM increased p27Kip1 expression by enhancing its mRNA steady state. This increase is not only a consequence of the DXM-induced interleukin 2 inhibition: we also found an increase in p27Kip1 mRNA stability that was not observed in quiescent lymphocytes. Cyclin/cyclin-dependent kinase (CDK) complexes immunoprecipitated with p27Kip1 are differentially modified by DXM addition: (a) G1 kinasic complexes (cyclin D/CDK4 or CDK6) associated with p27Kip1 are strongly decreased by DXM, (b) S-phase complexes (CDK2/cyclin E and A) remained stable or increased, and (c) the association of p27Kip1 with the phosphorylated forms of CDK1 is increased by DXM. In addition, CDK2 kinase activity was decreased in DXM-treated cells: we suggest that p27Kip1 might participate in inhibiting its catalytic activity. These results indicated that, in normal lymphoid cells, p27Kip1 may be involved in DXM antiproliferative effects. The increase of p27Kip1 expression and a decrease in G1 mitogenic factors, together with the redistribution of p27Kip1 to S/G2-M regulatory complexes, may explain the lengthening of G1 and S/G2 after DXM treatment in lymphocytes.