In-Plane and Out-of-Plane Investigation of Resonant Tunneling Polaritons in Metal-Dielectric-Metal Cavities.

Polaritons can be generated by tuning the optical transitions of a light emitter to the resonances of a photonic cavity. We show that a dye-doped cavity generates resonant tunneling polaritons with Epsilon-Near-Zero (ENZ) effective permittivity. We studied the polariton spectral dispersion in dye-doped metal-dielectric-metal (MDM) cavities as a function of the in-plane (k||) and out-of-plane (k⊥) components of the incident wavevector. The dependence on k|| was investigated through ellipsometry, revealing the ENZ modes. The k⊥ dependence was measured by varying the cavity thickness under normal incidence using a Surface Force Apparatus (SFA). Both methods revealed a large Rabi splitting well exceeding 100 meV. The SFA-based investigation highlighted the collective nature of strong coupling by producing a splitting proportional to the square root of the involved photons. This study demonstrates the possibility of generating ENZ polaritons and introduces the SFA as a powerful tool for the characterization of strong light-matter interactions.

Mussel adhesion: A fundamental perspective on factors governing strong underwater adhesion.

Protein-based underwater adhesives of marine organisms exhibit extraordinary binding strength in high salinity based on utilizing a variety of molecular interaction mechanisms. These include acid-base interactions, bidentate bindings or complex hydrogen bonding interactions, and electrochemical manipulation of interfacial bonding. In this Perspective, we briefly review recent progress in the field, and we discuss how interfacial electrochemistry can vary interfacial forces by concerted tuning of surface charging, hydration forces, and tuning of the interfacial ion concentration. We further discuss open questions, controversial findings, and new paths into understanding and utilizing redox-proteins and derived polymers for enhancing underwater adhesion in a complex salt environment.

Topological barriers to defect nucleation generate large mechanical forces in an ordered fluid.

Common fluids cannot sustain static mechanical stresses at the macroscopic scale because they lack molecular order. Conversely, crystalline solids exhibit long-range order and mechanical strength at the macroscopic scale. Combining the properties of fluids and solids, liquid crystal films respond to mechanical confinement by both flowing and generating static forces. The elastic response, however, is very weak for film thicknesses exceeding 10 nm. In this study, the mechanical strength of a fluid film was enhanced by introducing topological defects in a cholesteric liquid crystal, producing unique viscoelastic and optomechanical properties. The cholesteric was confined under strong planar anchoring conditions between two curved surfaces with sphere-sphere contact geometry similar to that of large colloidal particles, creating concentric dislocation loops. During surface retraction, the loops shrank and periodically disappeared at the surface contact point, where the cholesteric helix underwent discontinuous twist transitions, producing weak oscillatory surface forces. On the other hand, new loop nucleation was frustrated by a topological barrier during fluid compression, creating a metastable state. This generated exceptionally large forces with a range exceeding 100 nm as well as extended blueshifts of the photonic bandgap. The metastable cholesteric helix eventually collapsed under a high compressive load, triggering a stick-slip-like cascade of defect nucleation and twist reconstruction events. These findings were explained using a simple theoretical model and suggest a general approach to enhance the mechanical strength of one-dimensional periodic materials, particularly cholesteric colloid mixtures.

Understanding and Controlling Mode Hybridization in Multicavity Optical Resonators Using Quantum Theory and the Surface Forces Apparatus.

Optical fields in metal-dielectric multilayers display typical features of quantum systems, such as energy level quantization and avoided crossing, underpinned by an isomorphism between the Helmholtz and Schrödinger wave equations. This article builds on the fundamental concepts and methods of quantum theory to facilitate the understanding and design of multicavity resonators. It also introduces the surface forces apparatus (SFA) as a powerful tool for rapid, continuous, and extensive characterization of mode dispersion and hybridization. Instead of fabricating many different resonators, two equal metal-dielectric-metal microcavities were created on glass lenses and displaced relative to each other in a transparent silicone oil using the SFA. The fluid thickness was controlled in real time with nanometer accuracy from more than 50 µm to less than 20 nm, reaching mechanical contact between the outer cavities in a few minutes. The fluid gap acted as a third microcavity providing optical coupling and producing a complex pattern of resonance splitting as a function of the variable thickness. An optical wave in this symmetric three-cavity resonator emulated a quantum particle with nonzero mass in a potential comprising three square wells. Interference between the wells produced a 3-fold splitting of degenerate energy levels due to hybridization. The experimental results could be explained using the standard methods and formalism of quantum mechanics, including symmetry operators and the variational method. Notably, the interaction between square wells produced bonding, antibonding, and nonbonding states that are analogous to hybridized molecular orbitals and are relevant to the design of "epsilon-near-zero" devices with vanishing dielectric permittivity.

Analogy between periodic patterns in thin smectic liquid crystal films and the intermediate state of superconductors.

Spontaneous breaking of symmetry in liquid crystal (LC) films often reveals itself as a microscopic pattern of molecular alignment. In a smectic-A LC, the emergence of positional order at the transition from the nematic phase leads to periodic textures that can be used as optical microarrays, templates for soft lithography, and ordering matrices for the organization and manipulation of functional nanoparticles. While both 1d and 2d patterns have been obtained as a function of the LC film thickness and applied fields, the connection has not been made between pattern formation and the peculiar critical behavior of LCs at the nematic-smectic transition, still eluding a comprehensive theoretical explanation. In this article, we demonstrate that an intense bend distortion applied to the LC molecular director while cooling from the nematic phase produces a frustrated smectic phase with depressed transition temperature, and the characteristic 1d periodic texture previously observed in thin films and under applied electric fields. In light of De Gennes' analogy with the normal-superconductor transition of a metal, we identify the 1d texture as the equivalent of the intermediate state in type I superconductors. The bend distortion is analog to the magnetic field in metals and penetrates in the frustrated phase as an array of undercooled nematic domains, periodically intermixed with bend-free smectic-A domains. Our findings provide fundamental evidence for theories of the nematic-smectic transition, highlighting the deep connection between phase frustration and pattern formation, and perspectives on the design of functional smectic microarrays.

Adhesive Properties of Adsorbed Layers of Two Recombinant Mussel Foot Proteins with Different Levels of DOPA and Tyrosine.

Using a surface forces apparatus and an atomic force microscope, we characterized the adhesive properties of adsorbed layers of two recombinant variants of Perna viridis foot protein 5 (PVFP-5), the main surface-binding protein in the adhesive plaque of the Asian green mussel. In one variant, all tyrosine residues were modified into 3,4-dihydroxy-l-phenylalanine (DOPA) during expression using a residue-specific incorporation strategy. DOPA is a key molecular moiety underlying underwater mussel adhesion. In the other variant, all tyrosine residues were preserved. The layer was adsorbed on a mica substrate and pressed against an uncoated surface. While DOPA produced a stronger adhesion than tyrosine in contact with the nanoscopic Si3N4 probe of the atomic force microscope, the two variants produced comparable adhesion on the curved macroscopic mica surfaces of the surface forces apparatus. These findings show that the presence of DOPA is not a sufficient condition to generate strong underwater adhesion. Surface chemistry and contact geometry affect the strength and abundance of protein-surface bonds created during adsorption and surface contact. Importantly, the adsorbed protein layer has a random and dynamic polymer-network structure that should be optimized to transmit the tensile stress generated during surface separation to DOPA surface bonds rather than other weaker bonds.

Direct measurements of structural forces and twist transitions in cholesteric liquid crystal films with a surface force apparatus.

Using a surface force apparatus, a cholesteric liquid crystal was confined between two crossed cylindrical surfaces that induced strong planar anchoring and normal alignment of the chiral helix. The film thickness and total twist angle of the chiral molecular structure were simultaneously measured using multiple-beam optical interference. As the film thickness was increased and the chiral structure deformed, the twist angle remained almost unchanged until discontinuous changes occurred at critical distances that were equally spaced by one cholesteric half-pitch length. Structural deformations generated oscillatory elastic forces with periodically spaced maxima corresponding to twist transitions. These findings were reproduced using an equilibrium model of cholesteric confinement and force generation. The analysis indicates that the strength of the azimuthal surface anchoring on mica is high, exceeding 0.2 mJ m-2.

Multiple-beam optical interferometry of anisotropic soft materials nanoconfined with the surface force apparatus.

Soft anisotropic materials that change their macroscopic properties in response to external stimuli such as light, electric field, or pressure are central to several new directions of technology, including optics, micro-mechanics, and bioengineering. Responsiveness is fundamentally connected to the anisotropic ordering of the material's building blocks at the nanometer scale. Here we propose the surface force apparatus as a powerful tool for investigating optically anisotropic materials at the nanometer scale using multiple-beam optical interference, allowing for simultaneous determination of film thickness, alignment, and chiral rotation of the optical axis. We present a method based on 4 × 4 matrices for calculating the exact transmission and reflection coefficients for light incident normal to a planar optical multilayer comprising an arbitrary number of chiral anisotropic layers with the helical axis normal to the layer. The multilayer can also include uniform birefringent media, optical adsorbing (e.g., metals) and isotropic materials. We introduce a technique to analyze and interpret the complex multiple-beam interference patterns arising from such multilayers and demonstrate it for the case of a twisted nematic liquid crystal confined to nanoscale thickness with the surface force apparatus. The analysis opens the prospect of studying the effect of strong confinement on the structure and response of a wide class of anisotropic materials.

Transient viscous response of the human cornea probed with the Surface Force Apparatus.

Knowledge of the biomechanical properties of the human cornea is crucial for understanding the development of corneal diseases and impact of surgical treatments (e.g., corneal laser surgery, corneal cross-linking). Using a Surface Force Apparatus we investigated the transient viscous response of the anterior cornea from donor human eyes compressed between macroscopic crossed cylinders. Corneal biomechanics was analyzed using linear viscoelastic theory and interpreted in the framework of a biphasic model of soft hydrated porous tissues, including a significant contribution from the pressurization and viscous flow of fluid within the corneal tissue. Time-resolved measurements of tissue deformation and careful determination of the relaxation time provided an elastic modulus in the range between 0.17 and 1.43 MPa, and fluid permeability of the order of 10-13 m4/(N∙s). The permeability decreased as the deformation was increased above a strain level of about 10%, indicating that the interstitial space between fibrils of the corneal stromal matrix was reduced under the effect of strong compression. This effect may play a major role in determining the observed rate-dependent non-linear stress-strain response of the anterior cornea, which underlies the shape and optical properties of the tissue.

Optical vortices generated by edge dislocations in electro-convective instability arrays of nematic liquid crystals.

We demonstrated by means of interferometry that optical vortices can be generated by diffraction of a laser beam from a birefringent nematic liquid crystal that spontaneously creates a periodic array of electro-convective domains and edge dislocations under an applied electric field. The diffracted beam of order m produced by an elementary dislocation comprises a number |m| of distinct optical vortices, each with unit topological charge. Birefringent liquid crystal arrays provide a fast, convenient, and promising way of generating and studying optical vortices. The used materials are inexpensive, fabrication processes are simple, and both input polarization and applied field can be used as external controls to switch the optical vortices on and off.

Gastric mucus and mucuslike hydrogels: Thin film lubricating properties at soft interfaces.

Mucus is a viscous slime that plays a vital role in protecting and lubricating biological tissues, in particular, soft epithelium interfaces such as in the stomach, intestines, and esophagus. Previous attempts to generate mucus models that mimick or simulate its characteristics have been predominantly focused on the rheological properties. This study investigates both rheological and tribological shear properties of thin films of gastric mucus from a porcine source and its mimics at compliant soft interfaces. The lubricating efficacy of biological mucus and its mimics was observed to be superior at hydrophilic tribological interfaces compared to hydrophobic ones. Facile spreading of all mucus samples at hydrophilic steel-polydimethylsiloxane (PDMS) interfaces allowed for the retainment of the lubricating films over a wide range of speed, slide/roll ratio, and external load. In contrast, poor wetting at hydrophobic PDMS-PDMS interfaces led to depletion of the mucus samples from the interface with increasing speed. Among the different mucus models investigated in this study, fluid mixtures of commercially available porcine gastric mucin (PGM) and polyacrylic acid (PAA) displayed the most persistent lubricating effects under various tribological experimental conditions. A mixture of PGM and PAA holds a high potential as mucus mimic, not only for its rheological similarity, but also for its excellent lubricity in soft compliant and hydrophilic contacts.

Direct Measurement of the Surface Energy of Graphene.

Graphene produced by chemical vapor deposition (CVD) is a promising candidate for implementing graphene in a range of technologies. In most device configurations, one side of the graphene is supported by a solid substrate, wheras the other side is in contact with a medium of interest, such as a liquid or other two-dimensional material within a van der Waals stack. In such devices, graphene interacts on both faces via noncovalent interactions and therefore surface energies are key parameters for device fabrication and operation. In this work, we directly measured adhesive forces and surface energies of CVD-grown graphene in dry nitrogen, water, and sodium cholate using a modified surface force balance. For this, we fabricated large (∼1 cm2) and clean graphene-coated surfaces with smooth topography at both macro- and nanoscales. By bringing two such surfaces into contact and measuring the force required to separate them, we measured the surface energy of single-layer graphene in dry nitrogen to be 115 ± 4 mJ/m2, which was similar to that of few-layer graphene (119 ± 3 mJ/m2). In water and sodium cholate, we measured interfacial energies of 83 ± 7 and 29 ± 6 mJ/m2, respectively. Our work provides the first direct measurement of graphene surface energy and is expected to have an impact both on the development of graphene-based devices and contribute to the fundamental understanding of surface interactions.

Complexation and synergistic boundary lubrication of porcine gastric mucin and branched poly(ethyleneimine) in neutral aqueous solution.

Lubrication of soft polydimethylsiloxane (PDMS) elastomer interfaces was studied in aqueous mixtures of porcine gastric mucin (PGM) and branched polyethyleneimine (b-PEI) at neutral pH and various ionic strengths (0.1-1.0 M). While neither PGM nor b-PEI improved lubrication compared to polymer-free buffer solution, their mixtures produced a synergistic lubricating effect by reducing friction coefficients by nearly two orders of magnitude, especially at slow sliding speed in the boundary lubrication regime. An array of spectroscopic studies revealed that small cationic b-PEI molecules were able to strongly bind and penetrate into large anionic PGM molecules, producing an overall contraction of the randomly coiled PGM conformation. The interaction also affected the structure of the folded PGM protein terminals, decreased the surface potential and increased light absorbance in PGM:b-PEI mixtures. Adding an electrolyte (NaCl) weakened the aggregation between PGM and b-PEI, and degraded the lubrication synergy, indicating that electrostatic interactions drive PGM:b-PEI complexation.

Self-organized arrays of dislocations in thin smectic liquid crystal films.

Combining optical microscopy, synchrotron X-ray diffraction and ellipsometry, we studied the internal structure of linear defect domains (oily streaks) in films of a smectic liquid crystal 8CB with thicknesses in the range of 100-300 nm. These films are confined between air and a rubbed PVA polymer substrate which imposes hybrid anchoring conditions (normal and unidirectional planar, respectively). We show how the presence or absence of dislocations controls the structure of highly deformed thin smectic films. Each domain contains smectic layers curved in the shape of flattened hemicylinders to satisfy both anchoring conditions, together with grain boundaries whose size and shape are controlled by the presence of dislocation lines. A flat grain boundary normal to the interface connects neighboring hemicylinders, while a rotating grain boundary (RGB) is located near the axis of curvature of the cylinders. The RGB shape appears such that dislocation lines are concentrated at its summit close to the air interface. The smectic layers reach the polymer substrate via a transition region where the smectic layer orientation satisfies the planar anchoring conditions over the entire polymer substrate and whose thickness does not depend on that of the film. The strength of planar anchoring appears to be high, larger than 10(-2) mJ m(-2), compensating for the high energy cost of creating an additional 2D defect between a horizontal smectic layer and perpendicular ones of the transition region. This 2D defect may be melted, in order to avoid the creation of a transition region structure composed of a large number of dislocations. As a result, linear defect domains can be considered as arrays of oriented defects, straight dislocations of various Burger vectors, whose location is now known, and 2D nematic defects. The possibility of easy variation between the present structure with a moderate amount of dislocations and a structure with a large number of dislocations is also demonstrated.

Tailoring Anisotropic Interactions between Soft Nanospheres Using Dense Arrays of Smectic Liquid Crystal Edge Dislocations.

We investigated composite films of gold nanoparticles (NPs)/liquid crystal (LC) defects as a model system to understand the key parameters, which allow for an accurate control of NP anisotropic self-assemblies using soft templates. We combined spectrophotometry, Raman spectroscopy, and grazing incidence small-angle X-ray scattering with calculations of dipole coupling models and soft sphere interactions. We demonstrate that dense arrays of elementary edge dislocations can strongly localize small NPs along the defect cores, resulting in formation of parallel chains of NPs. Furthermore, we show that within the dislocation cores the inter-NP distances can be tuned. This phenomenon appears to be driven by the competition between "soft (nano)sphere" attraction and LC-induced repulsion. We evidence two extreme regimes controlled by the solvent evaporation: (i) when the solvent evaporates abruptly, the spacing between neighboring NPs in the chains is dominated by van der Waals interactions between interdigitated capping ligands, leading to chains of close-packed NPs; (ii) when the solvent evaporates slowly, strong interdigitation between the is avoided, leading to a dominating LC-induced repulsion between NPs associated with the replacement of disordered cores by NPs. The templating of NPs by topological defects, beyond the technological inquiries, may enable creation, investigation, and manipulation of unique collective features for a wide range of nanomaterials.

Mussel adhesion is dictated by time-regulated secretion and molecular conformation of mussel adhesive proteins.

Interfacial water constitutes a formidable barrier to strong surface bonding, hampering the development of water-resistant synthetic adhesives. Notwithstanding this obstacle, the Asian green mussel Perna viridis attaches firmly to underwater surfaces via a proteinaceous secretion (byssus). Extending beyond the currently known design principles of mussel adhesion, here we elucidate the precise time-regulated secretion of P. viridis mussel adhesive proteins. The vanguard 3,4-dihydroxy-L-phenylalanine (Dopa)-rich protein Pvfp-5 acts as an adhesive primer, overcoming repulsive hydration forces by displacing surface-bound water and generating strong surface adhesion. Using homology modelling and molecular dynamics simulations, we find that all mussel adhesive proteins are largely unordered, with Pvfp-5 adopting a disordered structure and elongated conformation whereby all Dopa residues reside on the protein surface. Time-regulated secretion and structural disorder of mussel adhesive proteins appear essential for optimizing extended nonspecific surface interactions and byssus' assembly. Our findings reveal molecular-scale principles to help the development of wet-resistant adhesives.

Ferric Ions Inhibit the Amyloid Fibrillation of ß-Lactoglobulin at High Temperature.

The energetics of amyloid fibrillar aggregation of ß-lactoglobulin (ßLG) following incubation at high temperature and acid pH was studied by differential scanning calorimetry in the presence of Cu(2+) or Fe(3+) cations, and without any metal. Cu(2+) and metal-free protein solutions showed a distinct exothermic response that disappeared almost completely when the Fe(3+) molar concentration was ten times greater than the ßLG concentration. Thioflavin T fluorescence studies in solution and atomic force microscopy analysis of the deposit left on flat mica substrates by heat-incubated ßLG solutions correlated the absence of exothermic response of Fe(3+)-ßLG solutions with a lack of fibril production. In contrast, abundant fibril deposits were observed for Cu(2+)-ßLG solutions, with a rich polymorphism of multistrand fibrillar structures. Electron paramagnetic resonance revealed that Fe(3+) permanently binds to ßLG in the aggregate state whereas Cu(2+) plays a catalytic role without binding to the protein. We propose that Fe(3+) inhibits fibril production after binding to a key region of the protein sequence, possibly interfering with the nucleation step of the fibrillation process and opening a nonfibrillar aggregation pathway. These findings suggest that transition metal ions can be utilized to effectively modulate protein self-assembly into a variety of structures with distinct morphologies at the nanoscale level.

Molecular Structure and Equilibrium Forces of Bovine Submaxillary Mucin Adsorbed at a Solid-Liquid Interface.

By combining dynamic light scattering, circular dichroism spectroscopy, atomic force microscopy, and surface force apparatus, the conformation of bovine submaxillary mucin in dilute solution and nanomechanical properties of mucin layers adsorbed on mica have been investigated. The samples were prepared by additional chromatographic purification of commercially available products. The mucin molecule was found to have a z-average hydrodynamic diameter of ca. 35 nm in phosphate buffered solution, without any particular secondary or tertiary structure. The contour length of the mucin is larger than, yet of the same order of magnitude as the diameter, indicating that the molecule can be modeled as a relatively rigid polymeric chain due to the large persistence length of the central glycosylated domain. Mucin molecules adsorbed abundantly onto mica from saline buffer, generating polymer-like, long-ranged, repulsive, and nonhysteretic forces upon compression of the adsorbed layers. Detailed analysis of such forces suggests that adsorbed mucins had an elongated conformation favored by the stiffness of the central domain. Acidification of aqueous media was chosen as means to reduce mucin-mucin and mucin-substrate electrostatic interactions. The hydrodynamic diameter in solution did not significantly change when the pH was lowered, showing that the large persistence length of the mucin molecule is due to steric hindrance between sugar chains, rather than electrostatic interactions. Remarkably, the force generated by an adsorbed layer with a fixed surface coverage also remained unaltered upon acidification. This observation can be linked to the surface-protective, pH-resistant role of bovine submaxillary mucin in the variable environmental conditions of the oral cavity.

Simultaneous measurements of molecular forces and electro-optical properties of a confined 5CB liquid crystal film using a surface forces apparatus.

Using a surface forces apparatus (SFA), we studied the forces associated with the reorientation of molecules of a common nematic thermotropic liquid crystal, 4'-n-pentyl-4-cyanobiphenyl (5CB), confined between two conducting (silver) surfaces and its optical behavior under the influence of electric fields with varying magnitudes and field directions. A transient attractive force was observed due to partial reorientations of the liquid crystal molecules and the flow of free ions, in addition to a stronger constant capacitance attraction between the silver surfaces. At the same time, the optical properties of the liquid crystals were observed perpendicular to the silver surfaces. Observations of shifts and fluctuations of the extraordinary wave of the (multiple beam) interference fringes measure the refractive index of the director component parallel to the surface, which is sensitive to tilt motion (or reorientation) of the liquid crystal molecules that provided details of the anisotropic orientations of the molecules and domains. Any lateral differential refractive index change is easily observed by optical microscopy. The optical microscope imaging showed that the changes in the optical properties are due to convective flow at domain boundaries of the liquid crystal molecules (and possible free ions) between the two charged surfaces. At low electric fields, propagation of domain boundaries was observed, while at higher electric fields, hexagonal patterns of flowing molecules were observed. The interplay of the force measurements and optical observations reveal a complex dynamic behavior of liquid crystals subjected to varying electric fields in confined spaces.

Modeling the optical properties of self-organized arrays of liquid crystal defects.

Local full Mueller matrix measurements in the Fourier plane of a microscope lens were used to determine the internal anisotropic ordering in periodic linear arrays of smectic liquid crystal defects, known as 'oily streaks'. We propose a single microstructure-dependent model taking into account the anisotropic dielectric function of the liquid crystal that reproduces the smectic layers orientation and organization in the oily streaks. The calculated Mueller matrix elements are compared to the measured data to reveal the anchoring mechanism of the smectic oily streaks on the substrate and evidence the presence of new type of defect arrangement. Beyond the scientific inquiry, the understanding and control of the internal structure of such arrays offer technological opportunities for developing liquid-crystal based sensors and self-assembled nanostructures.