Nuovi copolimeri triblocco biodegradabili a base di PLA per imballaggi alimentari

Nella presente Tesi si procede alla preparazione e caratterizzazione di nuovi poliesteri alifatici a base di PLLA che offrano garanzie di completa biodegradabilità e presentino caratteristiche chimico/fisiche adeguate ad applicazioni nell’ambito dell’imballaggio alimentare. La modifica chimica del PLLA è stata realizzata per introduzione in catena di segmenti opportunamente sintetizzati che fungono da iniziatori nell’apertura dell’anello di lattide nella ROP. I copolimeri triblocco, poli(lattico)-block-poli(propilene/neopentil glicole succinato) PLLAnP(PS80NS20)m, si differenziano per il diverso rapporto in peso tra i due diversi tipi di blocco, quello hard di PLLA e quello soft di P(PS80NS20). I risultati ottenuti sono di rilevante interesse applicativo: i copolimeri presentano migliorate proprietà meccaniche rispetto al PLLA, una maggiore velocità di biodegradazione, senza che abbia avuto luogo un peggioramento della stabilità termica e delle proprietà barriera, addirittura migliore al gas test O2

Magnetic Control of Transmission and Helicity of Nano-Structured Optical Beams in Magnetoplasmonic Vortex Lenses

We theoretically investigate the generation of far-field propagating optical beams with a desired orbital angular momentum by using an archetypical magnetoplasmonic tip surrounded by a gold spiral slit. The use of a magnetic material can lead to important implications once magneto-optical activity is activated through the application of an external magnetic field. The physical model and the numerical study presented here introduce the concept of magnetically tunable plasmonic vortex lens, namely a magnetoplasmonic vortex lens, which ensures a tunable selectivity in the polarization state of the generated nanostructured beam. The presented system provides a promising platform for a localized excitation of plasmonic vortices followed by their beaming in the far-field with an active modulation of both light's transmittance and helicity

Dynamics of magmatic intrusion: what can we learn from the comparison of analog and numerical models?

This study investigates the dynamics of magmatic intrusions based on the joint analysis of analog and numerical models. By injecting different fluids from the bottom of a solidified gelatin block, we simulate the propagation of magmatic intrusions through the crust and record their shapes, trajectories, and velocity as they rise towards the surface. Additionally, we make use of a 2D fluid-filled crack propagation model constrained by our experimental observations. The numerical simulations demonstrate that our viscous fluid-filled crack experiments, conducted with silicon-oil injections, propagate in the same regime as typical basaltic intrusions. The comparison between analog and numerical results allow us to define the domain of validity of the numerical model and its limit of applicability. This study provides new insights into the processes that control the propagation of magmatic intrusions and our ability to reproduce them using analog and numerical models

Switchable two-state plasmonic tweezers for dynamic manipulation of nano-objects

In this work we present a plasmonic platform capable of trapping nano-objects as small as 100 nm in two different spatial configurations. The switch between the two trapping states, localized on the tip and on the outer wall of a vertical gold nanochannel, can be activated by a variation in the focusing position of the excitation laser along the main axis of the nanotube. We show that the trapping mechanism is facilitated by both an electromagnetic and thermal action. The inner and outer trapping states are respectively characterized by a static and a dynamic behavior and their stiffness was measured by analyzing the position of the trapped specimens as a function of time. In addition, it was demonstrated that the stiffness of the static state is high enough to trap of particles as small as 40nm. These results show a simple, controllable way to generate a switchable two-state trapping regime, which could find applications as a model for the study of dynamic trapping or as mechanism for the development of nanofluidic devices

Hyperbolic Metamaterial Nanoparticles for Efficient Hyperthermia in the II and III Near-Infrared Windows

The use of gold nanoparticles for hyperthermia therapy in near infrared (NIR) spectral regions has catalysed substantial research efforts due to the potential impact in clinical therapy applications. However, the photoscattering effect scaling with the square of the nanoparticle volume leads to a low absorption efficiency, which has hindered the utility of gold nanoparticles in NIR II regions above 1000 nm. Here, we conquer this limit by introducing hyperbolic metamaterial nanoparticles that are made of multi-layered gold/dielectric nanodisks and exhibit >70% absorption efficiency in the NIR II and III regions. Their high light-to-heat conversion is demonstrated by a much larger temperature increase than that of gold nanodisks with the same amount of gold. Efficient in vitro hyperthermia of living cells with negligible cytotoxicity shows the potential of our approach for next-generation bio-medical applications

Hybrid plasmonic nanostructures based on controlled integration of MoS2 flakes on metallic nanoholes

Here, we propose an easy and robust strategy for the versatile preparation of hybrid plasmonic nanopores by means of controlled deposition of single flakes of MoS2 directly on top of metallic holes. The device is realized on silicon nitride commercial membranes and can be further refined by TEM or FIB milling to achieve the passing of molecules or nanometric particles through a pore. Importantly, we show that the plasmonic enhancement provided by the nanohole is strongly accumulated in the 2D nanopore, thus representing an ideal system for single-molecule sensing and sequencing in a flow-through configuration. Here, we also demonstrate that the prepared 2D material can be decorated with metallic nanoparticles that can couple their resonance with the nanopore resonance to further enhance the electromagnetic field confinement at the nanoscale level. This method can be applied to any gold nanopore with a high level of reproducibility and parallelization; hence, it can pave the way to the next generation of solid-state nanopores with plasmonic functionalities. Moreover, the controlled/ordered integration of 2D materials on plasmonic nanostructures opens a pathway towards new investigation of the following: enhanced light emission; strong coupling from plasmonic hybrid structures; hot electron generation; and sensors in general based on 2D materials. Nanopor

Pd/Au based catalyst immobilization in polymeric nanofibrous membranes via electrospinning for the selective oxidation of 5-hydroxymethylfurfural

Innovative nanofibrous membranes based on Pd/Au catalysts immobilized via electrospinning onto different polymers were engineered and tested in the selective oxidation of 5- (hydroxymethyl)furfural in an aqueous phase. The type of polymer and the method used to insert the active phases in the membrane were demonstrated to have a significant effect on catalytic performance. The hydrophilicity and the glass transition temperature of the polymeric component are key factors for producing active and selective materials. Nylon-based membranes loaded with unsupported metal nanoparticles were demonstrated to be more efficient than polyacrylonitrilebased membranes, displaying good stability and leading to high yield in 2,5-furandicarboxylic acid. These results underline the promising potential of large-scale applications of electrospinning for the preparation of catalytic nanofibrous membranes to be used in processes for the conversion of renewable molecules

lambda DNA through a plasmonic nanopore What can be detected by means of Surface Enhanced Raman Scattering?

Engineered electromagnetic fields in plasmonic nanopores enable enhanced optical detection and their use in single molecule sequencing. Here, a plasmonic nanopore prepared in a thick nanoporous film is used to investigate the interaction between the metal and a long-chain double strand DNA molecule. We discuss how the matrix of nanoporous metal can interact with the molecule thanks to: i) transient aspecific interactions between the porous surface and DNA and ii) optical forces exerted by the localized field in a metallic nanostructure. A duration of interaction up to tens of milliseconds enables to collect high signal-to-noise Raman vibrations allowing an easy label-free reading of information from the DNA molecule. Moreover, in order to further increase the event of detection rate, we tested a polymeric porous hydrogel placed beneath the solid-state membrane. This approach enables a slowdown of the molecule diffusion, thus increasing the number of detected interactions by a factor of about 20