Manipulating random lasing correlations in doped liquid crystals.

Random lasers are highly configurable light sources that are promising for imaging and photonic integration. In this study, random lasing action was generated by optically pumping N-(4-methoxybenzylidene)-4-butylaniline (MBBA) liquid crystals infiltrated with gold nanoparticles and a laser dye (pyrromethene 597 (PM597)). By varying the pump energy near a lasing threshold, we show that it is possible to control intensity correlations between random lasing modes. The correlations in the system were phenomenologically characterized using the Levy statistics of the emission spectrum survival function. We also find that correlations and persistence of lasing action are correlated. These results demonstrate the possibility to dynamically control a key physical feature of random lasers, which may find applications in biomedical settings and network communications.

Optical properties of metasurfaces infiltrated with liquid crystals.

Optical metasurfaces allow the ability to precisely manipulate the wavefront of light, creating many interesting and exotic optical phenomena. However, they generally lack dynamic control over their optical properties and are limited to passive optical elements. In this work, we report the nontrivial infiltration of nanostructured metalenses with three respective nematic liquid crystals of different refractive index and birefringence. The optical properties of the metalens are evaluated after liquid-crystal infiltration to quantify its effect on the intended optical design. We observe a significant modification of the metalens focus after infiltration for each liquid crystal. These optical changes result from modification of local refractive index surrounding the metalens structure after infiltration. We report qualitative agreement of the optical experiments with finite-difference time-domain solver (FDTD) simulation results. By harnessing the tunability inherent in the orientation dependent refractive index of the infiltrated liquid crystal, the metalens system considered here has the potential to enable dynamic reconfigurability in metasurfaces.

Iridium(III) Complex-Loaded Perfluoropropane Nanobubbles for Enhanced Sonodynamic Therapy.

Sonodynamic therapy (SDT) is a novel promising approach for the minimally invasive treatment of cancer derived from photodynamic therapy (PDT). In this study, we have explored an effective sonosensitizer for SDT by loading the iridium(III) complex [Ir(ppy)2(en)] OOCCH3, where ppy = 2-phenylpyridine and en = ethylenediamine], from now on referred to as Ir, with high photosensitizing ability, into echogenic nanobubbles (Ir-NBs). Akin to photosensitizers, sonosensitizers are acoustically activated by deep-tissue-penetrating low-frequency ultrasound (US) resulting in a localized therapeutic effect attributed to an excessive generation of reactive oxygen species (ROS). The Ir-NB formulation was optimized, and the in vitro characterizations were carried out, including physical properties, acoustic performance, intracellular ROS generation, and cytotoxicity against two human cancer cell lines. Ir-NBs had an average size of 303.3 ± 91.7 nm with a bubble concentration of 9.28 × 1010 particles/mL immediately following production. We found that the initial Ir feeding concentration had a negligible effect on the NB size, but affected the bubble concentration as well as the acoustic performance of the NBs. Through a combination of sonication and Ir-NBs treatment, an increase of 68.8% and 69.6% cytotoxicity in human ovarian cancer cells (OVCAR-3) and human breast cancer cells (MCF-7), respectively, was observed compared to the application of Ir-NBs alone. Furthermore, Ir-NBs exposed to the US also induced the highest levels of intracellular ROS generation compared to free Ir and free Ir with empty NBs. The combination of these results suggests that the differences in treatment efficacy is a direct result of acoustic cavitation. These results provide evidence that US activated Ir-loaded NBs have the potential to become an effective sonosensitizer for SDT.

Magneto-Optical Activity in Nonmagnetic Hyperbolic Nanoparticles.

Active nanophotonics can be realized by controlling the optical properties of materials with external magnetic fields. Here, we explore the influence of optical anisotropy on the magneto-optical activity in nonmagnetic hyperbolic nanoparticles. We demonstrate that the magneto-optical response is driven by the hyperbolic dispersion via the coupling of metallic-induced electric and dielectric-induced magnetic dipolar optical modes with static magnetic fields. Magnetic circular dichroism experiments confirm the theoretical predictions and reveal tunable magneto-optical activity across the visible and near infrared spectral range.

Hyperbolic Meta-Antennas Enable Full Control of Scattering and Absorption of Light.

We introduce a novel concept of hybrid metal-dielectric meta-antenna supporting type II hyperbolic dispersion, which enables full control of absorption and scattering of light in the visible/near-infrared spectral range. This ability lies in the different nature of the localized hyperbolic Bloch-like modes excited within the meta-antenna. The experimental evidence is corroborated by a comprehensive theoretical study. In particular, we demonstrate that two main modes, one radiative and one non-radiative, can be excited by direct coupling with the free-space radiation. We show that the scattering is the dominating electromagnetic decay channel, when an electric dipolar mode is induced in the system, whereas a strong absorption process occurs when a magnetic dipole is excited. Also, by varying the geometry of the system, the relative ratio of scattering and absorption, as well as their relative enhancement and/or quenching, can be tuned at will over a broad spectral range, thus enabling full control of the two channels. Importantly, both radiative and nonradiative modes supported by our architecture can be excited directly with far-field radiation. This is observed to occur even when the radiative channels (scattering) are almost totally suppressed, thereby making the proposed architecture suitable for practical applications. Finally, the hyperbolic meta-antennas possess both angular and polarization independent structural integrity, unlocking promising applications as hybrid meta-surfaces or as solvable nanostructures.

Cooperative Energy Transfer Controls the Spontaneous Emission Rate Beyond Field Enhancement Limits.

Quantum emitters located in proximity to a metal nanostructure individually transfer their energy via near-field excitation of surface plasmons. The energy transfer process increases the spontaneous emission (SE) rate due to plasmon-enhanced local field. Here, we demonstrate a significant acceleration of the quantum emitter SE rate in a plasmonic nanocavity due to cooperative energy transfer (CET) from plasmon-correlated emitters. Using an integrated plasmonic nanocavity, we realize up to sixfold enhancement in the emission rate of emitters coupled to the same nanocavity on top of the plasmonic enhancement of the local density of states. The radiated power spectrum retains the plasmon resonance central frequency and line shape, with the peak amplitude proportional to the number of excited emitters indicating that the observed cooperative SE is distinct from superradiance. Plasmon-assisted CET offers unprecedented control over the SE rate and allows us to dynamically control the spontaneous emission rate at room temperature which can enable SE rate based optical modulators.

Extreme sensitivity biosensing platform based on hyperbolic metamaterials.

Optical sensor technology offers significant opportunities in the field of medical research and clinical diagnostics, particularly for the detection of small numbers of molecules in highly diluted solutions. Several methods have been developed for this purpose, including label-free plasmonic biosensors based on metamaterials. However, the detection of lower-molecular-weight (<500 Da) biomolecules in highly diluted solutions is still a challenging issue owing to their lower polarizability. In this context, we have developed a miniaturized plasmonic biosensor platform based on a hyperbolic metamaterial that can support highly confined bulk plasmon guided modes over a broad wavelength range from visible to near infrared. By exciting these modes using a grating-coupling technique, we achieved different extreme sensitivity modes with a maximum of 30,000 nm per refractive index unit (RIU) and a record figure of merit (FOM) of 590. We report the ability of the metamaterial platform to detect ultralow-molecular-weight (244 Da) biomolecules at picomolar concentrations using a standard affinity model streptavidin-biotin.

All-optical guided-wave random laser in nematic liquid crystals.

Spatial solitons can affect and enhance random lasing in optically-pumped dyedoped nematic liquid crystals. Upon launching two collinear beams in the sample, the first to pump the fluorescent guest molecules and the second to induce a reorientational soliton, strikingly the second beam not only guides the emitted photons in the soliton waveguide, but also enhances the lasing efficiency and modulates its spectral width. By altering the scattering paths of the emitted photons, the soliton also contributes to the selection of the lasing modes, as further confirmed by the observed kinks in the input/output characteristics. These experimental results demonstrate that random lasing can be efficiently controlled by a light beam which does not interact with the gain molecules, opening a route towards light-controlled random lasers.

Interface of physics and biology: engineering virus-based nanoparticles for biophotonics.

Virus-based nanoparticles (VNPs) have been used for a wide range of applications, spanning basic materials science and translational medicine. Their propensity to self-assemble into precise structures that offer a three-dimensional scaffold for functionalization has led to their use as optical contrast agents and related biophotonics applications. A number of fluorescently labeled platforms have been developed and their utility in optical imaging demonstrated, yet their optical properties have not been investigated in detail. In this study, two VNPs of varying architectures were compared side-by-side to determine the impact of dye density, dye localization, conjugation chemistry, and microenvironment on the optical properties of the probes. Dyes were attached to icosahedral cowpea mosaic virus (CPMV) and rod-shaped tobacco mosaic virus (TMV) through a range of chemistries to target particular side chains displayed at specific locations around the virus. The fluorescence intensity and lifetime of the particles were determined, first using photochemical experiments on the benchtop, and second in imaging experiments using tissue culture experiments. The virus-based optical probes were found to be extraordinarily robust under ultrashort, pulsed laser light conditions with a significant amount of excitation energy, maintaining structural and chemical stability. The most effective fluorescence output was achieved through dye placement at optimized densities coupled to the exterior surface avoiding conjugated ring systems. Lifetime measurements indicate that fluorescence output depends not only on spacing the fluorophores, but also on dimer stacking and configurational changes leading to radiationless relaxation-and these processes are related to the conjugation chemistry and nanoparticle shape. For biological applications, the particles were also examined in tissue culture, from which it was found that the optical properties differed from those found on the benchtop due to effects from cellular processes and uptake kinetics. Data indicate that fluorescent cargos are released in the endolysosomal compartment of the cell targeted by the virus-based optical probes. These studies provide insight into the optical properties and fates of fluorescent proteinaceous imaging probes. The cellular release of cargo has implications not only for virus-based optical probes, but also for drug delivery and release systems.

Directed organization of DNA filaments in a soft matter template.

We have developed a noninvasive, all-optical, holographic technique for permanently aligning liquid crystalline DNA filaments in a microperiodic template realized in soft-composite (polymeric) materials. By combining optical intensity holography with a selective microfluidic etching process, a channelled microstructure has been realized which enables self-assembly of DNA. The striking chemicophysical properties of the structure immobilize the DNA filaments within the microchannels without the need of any kind of surface chemistry or functionalization. Polarized optical, confocal, and electronic microscopies have been used for characterizing the DNA geometry inside the microchannels in terms of birefringence, fluorescence, and nanoscale organization properties. In particular, observation of a far-field diffraction pattern confirms a periodic organization of the DNA filaments inside the polymeric template.

The interaction of tryptophan enantiomers with model membranes is modulated by polar head type and physical state of phospholipids.

The mutual influence of chiral bioactive molecules and supramolecular assemblies is currently being studied in many research fields, including medical-pharmaceutical applications. Model membranes of phospholipids, such as the zwitterionic dipalmitoylphosphatidylcholine (DPPC) and the anionic dipalmitoylphosphatidylglycerol (DPPG), interact with a variety of chiral compounds that include amino acids. In this work, the interaction of tryptophan enantiomers, L-Trp and D-Trp, on DPPC and DPPG bilayers was investigated by using differential scanning calorimetry, attenuated total reflectance-Fourier transform infrared and spin-label electron spin resonance spectroscopies as well as molecular docking simulations. The results show that Trp enantiomers slightly perturb the bilayer thermotropic phase transitions. For both membranes, O atoms in the carbonyl groups have a propensity to act as acceptors of a (weak) hydrogen bond. The Trp chiral forms also promote formation of hydrogen bonds and/or hydration in the PO2- moiety of the phosphate group, especially for the DPPC bilayer. In contrast, they interact more closely with the glycerol group of DPPG polar head. Only for DPPC bilayers, both enantiomers increase the packing of the first hydrocarbon chain segments for temperatures through the gel state, whereas they do not affect the lipid chain order and mobility in the fluid state. The results are consistent with a Trp association in the upper region of the bilayers without permeation in the innermost hydrophobic region. The findings suggest that neutral and anionic lipid bilayers are differently sensitive to amino acid chirality.

Chirality in Light-Matter Interaction.

The scientific effort to control the interaction between light and matter has grown exponentially in the last 2 decades. This growth has been aided by the development of scientific and technological tools enabling the manipulation of light at deeply sub-wavelength scales, unlocking a large variety of novel phenomena spanning traditionally distant research areas. Here, the role of chirality in light-matter interactions is reviewed by providing a broad overview of its properties, materials, and applications. A perspective on future developments is highlighted, including the growing role of machine learning in designing advanced chiroptical materials to enhance and control light-matter interactions across several scales.

Role of the Human Serum Albumin Protein Corona in the Antimicrobial and Photothermal Activity of Metallic Nanoparticles against Escherichia coli Bacteria.

The emergence of antibiotic-resistant bacteria has become a major public health concern, leading to growing interest in alternative antimicrobial agents. The antibacterial activity of metal nanoparticles (NPs) has been extensively studied, showing that they can effectively inhibit the growth of various bacteria, including both Gram-positive and -negative strains. The presence of a protein corona, formed by the adsorption of proteins onto the NP surface in biological fluids, can significantly affect their toxicity. Understanding the effect of the protein corona on the antimicrobial activity of metal NPs is crucial for their effective use as antimicrobial agents. In this study, the antimicrobial activity of noble metal NPs, such as platinum (Pt), silver (Ag), and gold (Au) with and without the human serum albumin (HSA) protein corona against Escherichia coli strains, was investigated. In addition, the plasmonic photothermal effect related to AuNPs, which resulted to be the most biocompatible compared to the other considered metals, was evaluated. The obtained results suggest that the HSA protein corona modulated the antimicrobial activity exerted by the metal NPs against E. coli bacteria. These findings may pave the way for the investigation and development of innovative nanoapproaches to face antibiotic resistance emergence.

Fano resonant optical coatings platform for full gamut and high purity structural colors.

Structural coloring is a photostable and environmentally friendly coloring approach that harnesses optical interference and nanophotonic resonances to obtain colors with a range of applications including display technologies, colorful solar panels, steganography, décor, data storage, and anticounterfeiting measures. We show that optical coatings exhibiting the photonic Fano Resonance present an ideal platform for structural coloring; they provide full color access, high color purity, high brightness, controlled iridescence, and scalable manufacturing. We show that an additional oxide film deposited on Fano resonant optical coatings (FROCs) increases the color purity (up to 99%) and color gamut coverage range of FROCs to 61% of the CIE color space. For wide-area structural coloring applications, FROCs have a significant advantage over existing structural coloring schemes.

All-Optical Tunability of Metalenses Permeated with Liquid Crystals.

Metasurfaces have been extensively engineered to produce a wide range of optical phenomena, allowing exceptional control over the propagation of light. However, they are generally designed as single-purpose devices without a modifiable postfabrication optical response, which can be a limitation to real-world applications. In this work, we report a nanostructured planar-fused silica metalens permeated with a nematic liquid crystal (NLC) and gold nanoparticle solution. The physical properties of embedded NLCs can be manipulated with the application of external stimuli, enabling reconfigurable optical metasurfaces. We report the all-optical, dynamic control of the metalens optical response resulting from thermoplasmonic-induced changes of the NLC solution associated with the nematic-isotropic phase transition. A continuous and reversible tuning of the metalens focal length is experimentally demonstrated, with a variation of 80 µm (0.16% of the 5 cm nominal focal length) along the optical axis. This is achieved without direct mechanical or electrical manipulation of the device. The reconfigurable properties are compared with corroborating numerical simulations of the focal length shift and exhibit close correspondence.

Fano-resonant ultrathin film optical coatings.

Optical coatings are integral components of virtually every optical instrument. However, despite being a century-old technology, there are only a handful of optical coating types. Here, we introduce a type of optical coatings that exhibit photonic Fano resonance, or a Fano-resonant optical coating (FROC). We expand the coupled mechanical oscillator description of Fano resonance to thin-film nanocavities. Using FROCs with thicknesses in the order of 300 nm, we experimentally obtained narrowband reflection akin to low-index-contrast dielectric Bragg mirrors and achieved control over the reflection iridescence. We observed that semi-transparent FROCs can transmit and reflect the same colour as a beam splitter filter, a property that cannot be realized through conventional optical coatings. Finally, FROCs can spectrally and spatially separate the thermal and photovoltaic bands of the solar spectrum, presenting a possible solution to the dispatchability problem in photovoltaics, that is, the inability to dispatch solar energy on demand. Our solar thermal device exhibited power generation of up to 50% and low photovoltaic cell temperatures (~30 °C), which could lead to a six-fold increase in the photovoltaic cell lifetime.

Hydrogen gas sensing using aluminum doped ZnO metasurfaces.

Hydrogen (H2) sensing is crucial in a wide variety of areas, such as industrial, environmental, energy and biomedical applications. However, engineering a practical, reliable, fast, sensitive and cost-effective hydrogen sensor is a persistent challenge. Here we demonstrate hydrogen sensing using aluminum-doped zinc oxide (AZO) metasurfaces based on optical read-out. The proposed sensing system consists of highly ordered AZO nanotubes (hollow pillars) standing on a SiO2 layer deposited on a Si wafer. Upon exposure to hydrogen gas, the AZO nanotube system shows a wavelength shift in the minimum reflectance by ∼13 nm within 10 minutes for a hydrogen concentration of 4%. These AZO nanotubes can also sense the presence of a low concentration (0.7%) of hydrogen gas within 10 minutes. Their rapid response time even for a low concentration, the possibility of large sensing area fabrication with good precision, and high sensitivity at room temperature make these highly ordered nanotube structures a promising miniaturized H2 gas sensor.

Biomolecular Sensing at the Interface between Chiral Metasurfaces and Hyperbolic Metamaterials.

In recent times, biomolecular sensing to recognize genetic fragments and proteins is spurring unprecedented interest as a diagnostic protocol for cancer and infectious diseases. Significant efforts have been made to design nanomaterials able to control the light-matter interaction at the single nanometer scale, where genes and proteins bind specifically to receptors. Here, we numerically show how the interface between a chiral metasurface and hyperbolic metamaterials can enable both high sensitivity and specificity for low-molecular-weight nucleic acids and proteins. As we have recently reported, hyperbolic dispersion metamaterials allow molecular biorecognition with extreme sensitivity because of coupled and highly confined plasmon polaritons. Specificity is almost exclusively achieved by receptor-ligand interaction at the in-plane sensing surface. Interestingly, an adapted out-of-plane chiral metasurface enables three key functionalities of the hyperbolic metamaterial sensor. Computational effort reveals that helicoidal metasurfaces can act as (i) efficient diffractive elements to excite surface and bulk plasmon polaritons; (ii) out-of-plane sensing branches to reduce the diffusion limit and increase the sensing surface; and (iii) biorecognition assay also via circular dichroism and chiral selectivity.

Coherent backscattering and dynamical light localization in liquid crystals driven throughout chaotic regimes.

An important effect of dynamical localization of light waves in liquid crystal electro-hydrodynamic instabilities is reported by investigating coherent backscattering effects. Recurrent multiple scattering in dynamic and chaotic complex fluids lead to a cone of enhanced backscattered light. The cone width and the related mean free path dependence on the dynamic scattering regimes emphasize the diverse light localization scales related to the internal structures present in the sample. The systems investigated up to now were mainly nano-powdered solutions or biological tissues, without any external control on the disorder. Here, an anisotropic complex fluid is "driven" throughout chaotic regimes by an external electric field, giving rise to dynamics that evolve through several spatio-temporal patterns.

Manipulating acoustic and plasmonic modes in gold nanostars.

In this contribution experimental evidence of plasmonic edge modes and acoustic breathing modes in gold nanostars (AuNSs) is reported. AuNSs are synthesized by a surfactant-free, one-step wet-chemistry method. Optical extinction measurements of AuNSs confirm the presence of localized surface plasmon resonances (LSPRs), while electron energy-loss spectroscopy (EELS) using a scanning transmission electron microscope (STEM) shows the spatial distribution of LSPRs and reveals the presence of acoustic breathing modes. Plasmonic hot-spots generated at the pinnacle of the sharp spikes, due to the optically active dipolar edge mode, allow significant intensity enhancement of local fields and hot-electron injection, and are thus useful for size detection of small protein molecules. The breathing modes observed away from the apices of the nanostars are identified as stimulated dark modes - they have an acoustic nature - and likely originate from the confinement of the surface plasmon by the geometrical boundaries of a nanostructure. The presence of both types of modes is verified by numerical simulations. Both these modes offer the possibility of designing nanoplasmonic antennas based on AuNSs, which can provide information on both mass and polarizability of biomolecules using a two-step molecular detection process.