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Scattering-type scanning near-field optical microscopy (s-SNOM) is currently regarded as a powerful tool for exploring important optical properties at nanoscale resolutions depending only on the size of a sharp tip that is scanned across the sample surface while being excited with a focused laser beam. Recently, it was shown that, among others, s-SNOM can quantitatively map the complex permittivity of materials and biological samples and hence other intrinsic related optical properties, such as the refractive index. In this work we apply this capability, previously demonstrated only at proof-of-concept level, in an experiment dealing with three distinct types of nanostructured materials: microcapsules for drug delivery assembled with layer-by-layer strategies, ultrathin optical coatings with controllable color properties, and plasmonic ceramic nanoparticles. We show that complex permittivity mapping with s-SNOM can contribute to the better understanding of such materials, providing information that is difficult or even impossible to assess with other techniques.

In this work, the preparation of a novel enzyme carrier based on a polymer multicomponent system was assessed. Indeed, the design of the above system considered several issues that are the need of applying a biodegradable polymer carrier, characterized by a nanometric dimension, thus suitable to diffuse into the dense mucus structure, with functionalities capable of interacting/reacting with enzymes but resistant to enzymatic degradation. The particles were prepared from solutions containing equimolar amount of highmolecular-weight poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) and by applying the nanoprecipitation method. Dynamic Light Scattering (DLS) measurements allowed to establish the optimal preparation conditions to obtain polymer particles characterized by diameters lower than 1 μm, which dimensions were confirmed by Field Emission Scanning Electron Microscope (FE-SEM) analysis. In order to produce surface functionalization, necessary for anchoring enzymes, the stereocomplexed particles, whose structuration was confirmed by Differential Scanning Calorimetry (DSC) measurements, underwent an amminolysis reaction by using a diamine as reactant. The treated particles were characterized by means of FE-SEM, Fourier-Transform Infrared Spectroscopy (FTIR), DLS and zeta potential measurements and their characteristics were compared with those of the neat PLLA/PDLA particles. The degree of functionalization turned out to depend on the applied conditions, it increasing by enhancing the reaction time. The activity of enzymes, i.e. papain and alginate lyase, anchored to the particles , was evaluated by Quartz Crystal Microbalance (QCM) and UV measurements.Moreover, with the aim at exploiting the material for an inhalation administration, a method to encapsulate the enzyme-particles systems was assessed. Conversely to free enzymes, the developed systems were found to be capable of diminishing the viscosity of two hydrogels, ad hoc prepared and based on the main constituents of the real mucus.

This work describes the preparation and characterization of printed biodegradable polymer (polylactic acid) capsules made in two different shapes: pyramid and rectangular capsules about 1 and 11 μm in size. Obtained core−shell capsules are described in terms of their morphology, loading efficiency, cargo release profile, cell cytotoxicity, and cell uptake. Both types of capsules showed monodisperse size and shape distribution and were found to provide sufficient stability to encapsulate small watersoluble molecules and to retain them for several days and ability for intracellular delivery. Capsules of 1 μm size can be internalized by HeLa cells without causing any toxicity effect. Printed capsules show unique characteristics compared with other drug delivery systems such as a wide range of possible cargoes, triggered release mechanism, and highly controllable shape and size.