New Horizons in Near-Zero Refractive Index Photonics and Hyperbolic Metamaterials.

The engineering of the spatial and temporal properties of both the electric permittivity and the refractive index of materials is at the core of photonics. When vanishing to zero, those two variables provide efficient knobs to control light-matter interactions. This Perspective aims at providing an overview of the state of the art and the challenges in emerging research areas where the use of near-zero refractive index and hyperbolic metamaterials is pivotal, in particular, light and thermal emission, nonlinear optics, sensing applications, and time-varying photonics.

Conflict and crime. Restorative justice in Italy.

The article presents a socio-legal analysis of the Legislative Decree (Lgs.D.) of 10 October 2022, n.150, implementing the law of 27 September 2021, n.134 (so-called "Cartabia reform"), which provides for the introduction in Italy of a comprehensive framework regulation of restorative justice. The central theme of this paper is precisely the conflict connected to a crime, the offender-victim relationship and restorative justice in the light of the aforementioned decree. As Luhmann observes, the omnipresence of conflicts in society is self-evident. Even the crime produces a conflict or, at times, is the extreme expression of a pre-existing and sometimes latent conflict. The problem that arises is, therefore, that of the control and management of conflicts. These are usually managed by the law, but, given its limitations, it is increasingly necessary to encourage the use of restorative justice programs. On an interpersonal level, conflict triggers a negative mechanism of hostility and disavowal of the other, which either wraps itself in an explosive vortex, or deviates, becoming the pretext for abandoning the only form of communication that conflict makes possible, as Luhmann observes, the one based on "no". The Italian regulatory intervention certainly appears relevant, albeit with some critical issues, and to be kept under observation for future application developments.

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.

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.

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.

Effect of the Combination of Gold Nanoparticles and Polyelectrolyte Layers on SERS Measurements.

In this study, polyelectrolyte (PE) layers are deposited on substrates made by glass covered with an array of gold nanoparticles (GNPs). In particular, the samples studied have 0 PE layers (GGPE0), 3 PE layers (GGPE3), 11 PE layers (GGPE11), and 21 PE layers (GGPE21). All samples have been studied by micro-Raman spectroscopy. An acetic acid solution (10% v/v) has been used as a standard solution in order to investigate the SERS effect induced by different numbers of PE layers in each sample. The Surface Enhancement Raman Spectroscopy (SERS) effect correlating to the number of PE layers deposited on the samples has been shown. This effect is explained in terms of an increase in the interaction between the photon of the laser source and the plasmonic band of the GNPs due to a change of the permittivity of the surrounding medium around the GNPs. The trends of the ratios of the intensities of the Raman bands of the acetic acid solution (acetic acid and water molecules) on the band at 1098 cm-1 ascribed to the substrates increase, and the number of PE layers increases.

Plasmonic Metasurfaces Based on Pyramidal Nanoholes for High-Efficiency SERS Biosensing.

An inverted pyramidal metasurface was designed, fabricated, and studied at the nanoscale level for the development of a label-free pathogen detection on a chip platform that merges nanotechnology and surface-enhanced Raman scattering (SERS). Based on the integration and synergy of these ingredients, a virus immunoassay was proposed as a relevant proof of concept for very sensitive detection of hepatitis A virus, for the first time to our best knowledge, in a very small volume (2 µL), without complex signal amplification, allowing to detect a minimal virus concentration of 13 pg/mL. The proposed work aims to develop a high-flux and high-accuracy surface-enhanced Raman spectroscopy (SERS) nanobiosensor for the detection of pathogens to provide an effective method for early and easy water monitoring, which can be fast and convenient.

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.

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.

A comprehensive optical analysis of nanoscale structures: from thin films to asymmetric nanocavities.

A simple and robust method able to evaluate and predict, with high accuracy, the optical properties of single and multi-layer nanostructures is presented. The method was implemented using a COMSOL Multiphysics simulation platform and it has been validated by four case studies with increasing numerical complexities: (i) a single thin layer (20 nm) of Ag deposited on a glass substrate; (ii) a metamaterial composed of five bi-layers of Ag/ITO (indium tin oxide), with a thickness of 20 nm each; (iii) a system based on a three-material unit cell (AZO/ITO/Ag), but without any thickness periodicity (AZO stands for Al2O3/zinc oxide); (iv) an asymmetric nanocavity (thin-ITO/Ag/thick-ITO/Ag). A thorough study of this latter configuration reveals peculiar metamaterial effects that can widen the actual scenario in nanophotonic applications. Numerical results have been compared with experimental data provided by real ellipsometric measurements performed on the above mentioned ad hoc fabricated nanostructures. The obtained agreement is excellent, suggesting this research as a valid design approach to realize multi-band metamaterials able to work in a broad spectral range.

Tensile control of the thermal flow in plasmonic heaters realized on flexible substrates.

In this paper, we present a simple and robust numerical method capable of predicting, with high accuracy, the thermal effects occurring for different gold nanoparticle arrangements under externally applied strain. The physical system is numerically implemented in the COMSOL Multiphysics simulation platform. The photothermal response of different arrangements of gold nanoparticles, resonantly excited by linearly polarized light, is considered with the system at rest and under the action of mechanical stress. The generation of heat at the nanoscale is analyzed by considering how this is affected by the variation of the extinction cross section. We describe the peculiar conditions under which mechanically controlled gold nanoparticle arrangements can significantly increase the local temperature due to the formation of localized photothermal hot spots. The resulting systems are envisioned in applications as optomechanically tunable plasmonic heaters.

Flexible thermo-plasmonics: an opto-mechanical control of the heat generated at the nanoscale.

The opto-mechanical control of the heat generated by an amorphous arrangement of homogenously distributed gold nanoparticles (AuNPs), excited by an external laser source, is investigated. Application of a macroscopic mechanical strain to the biocompatible elastomeric tape supporting the particles leads to a nanoscale modification of their mutual inter-distance. The resulting strong variation of the particles near-field coupling gives rise to a macroscopic variation of the photo-generated heat. A fine control of the amount of generated heat is thus possible by stretching the initially isotropic sample by only a few percent. Due to the anisotropy of the stretching procedure, the plasmon band shift and thus the heat generation becomes strongly polarization-dependent. A model of the system based on Mie theory is implemented by using a finite element method. Under optical excitation, two configurations of AuNPs, representing the same cluster of particles at rest and under stretching, show a relative increase of temperature that is in good quantitative agreement with experimental data, if normalized to the number of involved particles. This system realizes for the first time an opto-mechanical control of the temperature at the nanoscale which holds promise for the development of optically-active thermal patches, usable for biomedical applications, and flexible platforms for microfluidics and lab-on-a-chip devices.

Assessment of EtQxBox complexation in solution by steady-state and time-resolved fluorescence spectroscopy.

Reliable chemical sensors with high selectivity and sensitivity toward specific target molecules require rational synthesis of receptors, in-depth characterization of their complexation abilities and highly efficient transduction of the molecular recognition event. Here we report a steady-state and time-resolved fluorescence investigation of EtQxBox, a fluorescent conformationally blocked quinoxaline-based cavitand, aimed at assessing its selectivity toward aromatic versus non-aromatic analytes in solution. Fluorescence quenching of the EtQxBox in acetone is observed at increasing concentration of both aromatic (i.e. benzonitrile) and aliphatic (i.e. acetonitrile) compounds. The combination with fluorescence lifetime measurements permits to discriminate the predominantly static quenching of the aromatic analyte, due to non-fluorescent host-guest complex formation, from the mostly dynamic quenching of the non-aromatic compound, resulting from aspecific diffusive collisions between the fluorophore and the quencher. The equilibrium association constants for both the complexes have been estimated using Stern-Volmer model.

Plasmon-mediated cancer phototherapy: the combined effect of thermal and photodynamic processes.

A nanoplatform for simultaneous cellular imaging, and photodynamic and photothermal therapies has been designed and realized by embedding a purposely synthesized highly luminescent water soluble iridium(iii) compound into gold core-silica shell nanoparticles. These multifunctionalities arise mainly from the photophysical properties of the cyclometalated complex: (i) the heavy atom promotes, through excited triplet state formation, energy transfer processes towards molecular oxygen, with the generation of 1O2 (photodynamic effect); (ii) the overlap of the iridium(iii) complex emission band with the plasmonic resonance of gold nanostructures allows excitation energy transfer towards the metallic core (photothermal effect); (iii) the remarkable iridium(iii) complex luminescence feature, which is preserved despite energy transfer processes, makes the whole system an efficient luminescent bio-probe (imaging). Photophysical and photothermal investigations have been carried out, whereas in vitro photo-cytotoxicity tests have been performed on human glioblastoma cells (U87MG), highlighting significant cancer cell death at a very low photosensitizer concentration (<0.5 µM), by means of a synergistic photodynamic and photothermal effect.

Conformal Silk-Azobenzene Composite for Optically Switchable Diffractive Structures.

The use of biomaterials as optical components has recently attracted attention because of their ease of functionalization and fabrication, along with their potential use when integrated with biological materials. We present here an observation of the optical properties of a silk-azobenzene material (Azosilk) and demonstrate the operation of an Azosilk/PDMS composite structure that serves as a conformable and switchable optical diffractive structure. Characterization of thermal and isomeric properties of the device, along with its overall performance, is presented in terms of diffractive characteristics and response times. The ease of manufacturing and functionalization opens a promising avenue for rapid device prototyping and interfaces of expanded utility.

Photo-thermal effects in gold nanoparticles dispersed in thermotropic nematic liquid crystals.

The last few years have seen a growing interest in the ability of metallic nanoparticles (MNPs) to control temperature at the nanoscale. Under a suitable optical radiation, MNPs feature an enhanced light absorption/scattering, thus turning into an ideal nano-source of heat, remotely controllable by means of light. In this framework, we report our recent efforts on modeling and characterizing the photo-thermal effects observed in gold nanoparticles (GNPs) dispersed in thermotropic Liquid Crystals (LCs). Photo-induced temperature variations in GNPs dispersed in Nematic LCs (NLCs) have been studied by implementing an ad hoc theoretical model based on the thermal heating equation applied to an anisotropic medium. Theoretical predictions have been verified by performing photo-heating experiments on a sample containing a small percentage of GNPs dispersed in NLCs. Both theory and experiments represent an important achievement in understanding the physics of heat transfer at the nanoscale, with applications ranging from photonics to nanomedicine.