Green Synthesis of Iridium Nanoparticles from Winery Waste and Their Catalytic Effectiveness in Water Decontamination.

An environmentally friendly procedure was adopted for the first time to prepare green iridium nanoparticles starting from grape marc extracts. Grape marcs, waste of Negramaro winery production, were subjected to aqueous thermal extraction at different temperatures (45, 65, 80, and 100 °C) and characterized in terms of total phenolic contents, reducing sugars, and antioxidant activity. The results obtained showed an important effect of temperature with higher amounts of polyphenols and reducing sugars and antioxidant activity in the extracts with the increase of temperature. All four extracts were used as starting materials to synthesize different iridium nanoparticles (Ir-NP1, Ir-NP2, Ir-NP3, and Ir-NP4) that were characterized by Uv-Vis spectroscopy, transmission electron microscopy, and dynamic light scattering. TEM analysis revealed the presence of very small particles in all samples with sizes in the range of 3.0-4.5 nm with the presence of a second fraction of larger nanoparticles (7.5-17.0 nm) for Ir-NPs prepared with extracts obtained at higher temperatures (Ir-NP3 and Ir-NP4). Since the wastewater remediation of toxic organic contaminants on catalytic reduction has gained much attention, the application of the prepared Ir-NPs as catalysts towards the reduction of methylene blue (MB), chosen as the organic dye model, was evaluated. The efficient catalytic activity of Ir-NPs in the reduction of MB by NaBH4 was demonstrated and Ir-NP2 was prepared using the extract obtained at 65 °C, showing the best catalytic performance, with a rate constant of 0.527 ± 0.012 min-1 and MB reduction of 96.1% in just six min, with stability for over 10 months.

Disposable Molecularly Imprinted Polymer-Modified Screen-Printed Electrodes for Rapid Electrochemical Detection of l-Kynurenine in Human Urine.

l-Kynurenine (l-Kyn) is an endogenous metabolite produced in the catabolic route of l-Tryptophan (l-Trp), and it is a potential biomarker of several immunological disorders. Thus, the development of a fast and cheap technology for the specific detection of l-Kyn in biological fluids is of great relevance, especially considering its recent correlation with SARS-CoV-2 disease progression. Herein, a disposable screen-printed electrode based on a molecularly imprinted polymer (MIP) has been constructed: the o-Phenylenediamine monomer, in the presence of l-Kyn as a template with a molar ratio of monomer/template of 1/4, has been electropolymerized on the surface of a screen-printed carbon electrode (SPCE). The optimized kyn-MIP-SPCE has been characterized via cyclic voltammetry (CV), using [Fe(CN)6)]3-/4- as a redox probe and a scanning electron microscopy (SEM) technique. After the optimization of various experimental parameters, such as the number of CV electropolymerization cycles, urine pretreatment, electrochemical measurement method and incubation period, l-Kyn has been detected in standard solutions via square wave voltammetry (SWV) with a linear range between 10 and 100 µM (R2 = 0.9924). The MIP-SPCE device allowed l-Kyn detection in human urine in a linear range of 10-1000 µM (R2 = 0.9902) with LOD and LOQ values of 1.5 and 5 µM, respectively. Finally, a high selectivity factor α (5.1) was calculated for l-Kyn toward l-Trp. Moreover, the Imprinting Factor obtained for l-Kyn was about seventeen times higher than the IF calculated for l-Trp. The developed disposable sensing system demonstrated its potential application in the biomedical field.

Design of vanadium-dioxide-based resonant structures for tunable optical response.

Phase change materials are suitable for tunable photonic devices where the optical response can be altered under external stimuli, such as heat, an electrical or an optical signal. In this scenario, we performed numerical simulations to study the optical properties of a flat unpatterned resonant structure and a grating, both coated with a thin film of vanadium dioxide (VO2). Our results suggest that it is possible to modulate broadband and narrowband reflectance spectra of the resonant structures in the visible to near-infrared range by more than 40 % when the VO2 undergoes an insulator-to-metal phase transition. Resonant devices with a tunable spectral response may find application in sensors, filters, absorbers, and detectors.

High transmission from 2D periodic plasmonic finite arrays with sub-20 nm gaps realized with Ga focused ion beam milling.

Fabricating plasmonic nanostructures with good optical performances often requires lengthy and challenging patterning processes that can hardly be transferred to unconventional substrates, such as optical fiber tips or curved surfaces. Here we investigate the use of a single Ga focused ion beam process to fabricate 2D arrays of gold nanoplatelets for nanophotonic applications. While observing that focused ion beam milling of crossing tapered grooves inherently produces gaps below 20 nm, we provide experimental and theoretical evidence for the spectral features of grooves terminating with a sharp air gap. We show that transmission near 10% can be obtained via two-dimensional nano-focusing in a finite subset of 2D arrays of gold nanoplatelets. This enables the application of our nanostructure to detect variations in the refractive index of thin films using either reflected or transmitted light when a small number of elements are engaged.

Localized surface plasmon resonances in gold nano-patches on a gallium nitride substrate.

In this paper we describe the design, fabrication and characterization of gold nano-patches, deposited on gallium nitride substrate, acting as optical nanoantennas able to efficiently localize the electric field at the metal-dielectric interface. We analyse the performance of the proposed device, evaluating the transmission and the electric field localization by means of a three-dimensional finite difference time domain (FDTD) method. We detail the fabrication protocol and show the morphological characterization. We also investigate the near-field optical transmission by means of scanning near-field optical microscope measurements, which reveal the excitation of a localized surface plasmon resonance at a wavelength of 633 nm, as expected by the FDTD calculations. Such results highlight how the final device can pave the way for the realization of a single optical platform where the active material and the metal nanostructures are integrated together on the same chip.

Experimental demonstration of a novel bio-sensing platform via plasmonic band gap formation in gold nano-patch arrays.

In this paper we discuss the possibility of implementing a novel bio-sensing platform based on the observation of the shift of the leaky surface plasmon mode that occurs at the edge of the plasmonic band gap of metal gratings, when an analyte is deposited on top of the metallic structure. We report numerical calculations, fabrication and experimental measurements to prove the sensing capability of a two-dimensional array of gold nano-patches in the detection of a small quantity of Isopropyl Alcohol (IPA) deposited on top of sensor surface. The calculated sensitivity of our device approaches a value of 1000 nm/RIU with a corresponding Figure of Merit (FOM) of 222 RIU(-1). The presence of IPA can also be visually estimated by observing a color variation in the diffracted field. We show that color brightness and intensity variations can be ascribed to a change in the aperture size, keeping the periodicity constant, and to different types of analyte deposited on the sample, respectively. Moreover, we demonstrate that unavoidable fabrication imperfections revealed by the presence of rounded corners and surface roughness do not significantly affect device performance.

High-Purcell-factor dipolelike modes at visible wavelengths in H1 photonic crystal cavity.

The optimization of H1 photonic crystal cavities for applications in the visible spectral range is reported, with the goal to obtain a versatile photonic platform to explore strongly and weakly coupled systems. The resonators have been realized in silicon nitride and weakly coupled to both organic (fluorophores) and inorganic (colloidal nanocrystals) nanoparticles emitting in the visible spectral range. The theoretical Purcell factor of the two dipolelike modes in the defect has been increased up to approximately 90, and the experimental quality factor was measured to be approximately 750.

Optical filter based on two coupled PhC GaAs-membranes.

We demonstrate an ultracompact optical filter based on two coupled high-index contrast GaAs photonic crystal (PhC) membranes. The PhC membranes consist of a square lattice of air holes and behave as a Fabry-Perot cavity whose reflectivity and transmissivity depend on the air gap between the two membranes. The normal-incidence reflectance measurements and the numerical simulation of reflection spectra show a high sensitivity to the geometrical parameters, such as the distance between the slabs, whose control would make the device suitable for a new class of tunable optical filters.

Integration of grating couplers with a compact photonic crystal demultiplexer on an InP membrane.

We demonstrate the integration of a 30% efficient grating coupler with a compact photonic crystal wavelength demultiplexer (DeMUX). The DeMUX has seven output channels that are spaced 10 nm apart and is aimed at coarse WDM applications. The integrated devices are realized on a high-index-contrast InP membrane using a simple benzocyclobutene wafer bonding technique. Cross talks of -10 to -12 dB for four channels 20 nm apart are obtained without optimization.