Paolo Camorani

Electrochemical control of the conductivity in an organic memristor: a time-resolved X-ray fluorescence study of ionic drift as a function of the applied voltage.

Grazing-incidence X-ray fluorescence measurements were applied for a time-resolved study of an organic memristor conductivity variation mechanism. A comparison of these results with electrical measurements has allowed us to conclude that the variation of the fluorescence intensity of Rb ions is directly connected to the ionic charge transferred between the conducting polymer and the solid electrolyte, which made up the device. In addition, the conductivity of the memristor was shown to be a function of the transferred ionic charge.

Non-equilibrium electrical behaviour of polymeric electrochemical junctions

Current oscillations were observed at constant applied voltage in electrochemical heterostructures, composed of conducting polymer, solid electrolyte and a charge accumulating system (graphite electrode or capacitor). These oscillations were attributed to the periodic modulation of the conductivity in the active zone of conducting polymer (polyaniline) due to ionic flow in the solid electrolyte (polyethylene oxide with LiClO4).

Modeling and simulating the adaptive electrical properties of stochastic polymeric 3D networks

Memristors are passive two-terminal circuit elements that combine resistance and memory. Although in theory memristors are a very promising approach to fabricate hardware with adaptive properties, there are only very few implementations able to show their basic properties. We recently developed stochastic polymeric matrices with a functionality that evidences the formation of self-assembled three-dimensional (3D) networks of memristors. We demonstrated that those networks show the typical hysteretic behavior observed in the ‘one input-one output’ memristive configuration. Interestingly, using different protocols to electrically stimulate the networks, we also observed that their adaptive properties are similar to those present in the nervous system. Here, we model and simulate the electrical properties of these selfassembled polymeric networks of memristors, the topology of which is defined stochastically. First, we show that the model recreates the hysteretic behavior observed in the real experiments. Second, we demonstrate that the networks modeled indeed have a 3D instead of a planar functionality. Finally, we show that the adaptive properties of the networks depend on their connectivity pattern. Our model was able to replicate fundamental qualitative behavior of the real organic 3D memristor networks; yet, through the simulations, we also explored other interesting properties, such as the relation between connectivity patterns and adaptive properties. Our model and simulations represent an interesting tool to understand the very complex behavior of self-assembled memristor networks, which can finally help to predict and formulate hypotheses for future experiments.

Stochastic hybrid 3D matrix: learning and adaptation of electrical properties

Memristive devices are electronic elements with memory properties. This feature marks them out as possible candidates for mimicking synapse properties. Development of systems capable of performing simple brain operations demands a high level of integration of elements and their 3D organization into networks. Here, we demonstrate the formation and electrical properties of stochastic polymeric matrices. Several features of the network revealed similarities with those of the nervous system. In particular, applying different training protocols, we obtained two kinds of learning comparable to the “baby” and “adult” learning in animals and humans. To mimic “adult” learning, multi-task training was applied simultaneously resulting in the formation of few parallel pathways for a given task, modifiable by successive training. To mimic “baby” learning (imprinting), single task training was applied at one time, resulting in the formation of multiple parallel signal pathways, scarcely influenced by successive training.

Conducting polymer—solid electrolyte fibrillar composite material for adaptive networks

The non-linear electrical characteristics of a polymeric electrochemically controlled junction based on a conducting polymer (polyaniline) and a solid electrolyte (Li doped polyethylene oxide) are considered as basic features for the realization of smart materials based on the statistical occurrence of such heterojunctions in statistical networks. In this paper we demonstrate the possibility of realizing such adaptive networks in a statistically mixed polymeric fibrillar heterostructure.

Azo-Containing Polymer Brushes: Photoalignment and Application as Command Surfaces

A brush polymer containing photosensitive mesogenic side chains has been directly synthesized on glass substrates by a grafting method involving polymerization of a metacrylic azobenzenic monomer under Atomic Transfer Radical Polymerization (ATRP) conditions. Brush polymer surfaces, with respect to more traditional films, are resistant to solvents and to high temperatures due to the covalent bonds between chain and substrate, which stabilizes the film morphology. The peculiar characteristics of the present polymeric brushes, namely the intrinsic in-plane orientation of the mesogenic units located in the side chains, together with the possibility of a fine control on the structure, make them very attractive for application as command surfaces. We then employed such brushes as photo-controllable command surfaces in twisted/planar switchable cells filled with a low molecular weight liquid crystal and we characterized the molecular order at interface by means of confocal polarized Raman microscopy.

Doping-Induced Conductivity Transitions in Molecular Layers of Polyaniline: Optical Studies of Electronic State Changes

The doping-induced conductivity transitions in molecular layers of polyaniline have been studied by monitoring the correlated optical and spectroscopic changes using spectroscopic and single wavelength extinction ellipsometry, also in total internal reflection mode (TIRE), together with reflection spectrometry. The measurements were performed on deposited multilayers as well as on a Langmuir monolayer at the air-water interface, as a function of acidic doping. We found that the characteristic spectroscopic features of conducting and insulating polyaniline persisted down to the single layer, both in the solid state and at the air-water interface. We also investigated in real time the modulation of conductivity induced by the intercalation of Li ions in the polyaniline film, by a combination of time-resolved ellipsometry and reflectivity spectra measurements. In this case, the enhanced sensitivity provided by the TIRE geometry, combined with the relatively fast time scale accessible by the single wavelength ellipsometry, allowed us to follow in detail in real time the doping/dedoping process.

Photoinduced Morphological Changes and Optical Writing in a Liquid Crystalline Polymer on the Micron and Sub-Micron Scale

In this paper we describe our recent work on optical effects due to photoinduced molecular reorientation in a side chain liquid crystalline polymer, namely azo-polymethacrylate (PMA4). We have studied several kinds of optical effects on space scales ranging from the nanoscopic to macroscopic. In particular, we have built a computer controlled microscope-based apparatus to study photoinduced effects down to the micron scale in thin and ultrathin (Langmuir Blodgett) films of our material. Furthermore we measured the morphology and the photoinduced surface deformation by Atomic Force Microscopy in the submicron scale.

Raman spectroscopy application in frozen carrot cooked in different ways and the relationship with carotenoids

BACKGROUND Raman spectroscopy, in its confocal micro-Raman variation, has been recently proposed as a spatially resolved method to identify carotenoids in various food matrices, being faster, non-destructive, and avoiding sample extraction, but no data are present in the literature concerning its application to the evaluation of carotenoid pattern changes after thermal treatment of carrots. RESULTS The effect of three cooking methods (i.e. boiling, steaming and microwaving) was evaluated on frozen carrot, comparing changes on carotenoid profiles measured by means of Raman spectroscopy with their high-performance liquid chromatographic determination and colour. A more pronounced detrimental effect on carotenoids was detected in steamed carrots, in accordance with colour data. Conversely, boiling and, to a lesser extent, microwaving caused an increase in carotenoid concentration. Cooking procedures affected the Raman spectral features of carotenoids, causing a shift of vibration frequencies towards a higher energy, increase in the spectral baseline and peak intensities as well as a broadening of their width, probably in relation to the thermal degradation of longer carotenoids (i.e. the all-trans form) and the isomerization process. In particular, steamed samples showed a significantly higher increase of centre frequency, in accordance with a more pronounced isomerization and changes in colour parameters. CONCLUSION This work showed that the evolution of Raman spectral parameters could provide information on carotenoid bioaccessibility for carrots cooked using various methods. This paves the way for a future use of this technique to monitor and optimize cooking processes aimed at maximizing carotenoid bioaccessibility and bioavailability.

Optical Bit Stability and Relaxation Processes in a Liquid Crystal Polymer with a Photosensitive Azo Dye Molecule as Side Group

We present a study of optically-induced molecular relaxation and optical writing processes in a photosensitive liquid crystalline polymer, containing the azobenzene moiety in the side chain. Linear and non linear ESR spectroscopies, thermal analysis and rheology investigations carried on azo polymethacrylate (PMA) samples subjected to different thermal treatments have allowed to single out a suitable procedure to get stable, homogeneous substrates. Optical studies on micrometer length scale, adopting the selected procedure, have confirmed the stability conditions in both unaligned and aligned samples. The temperature dependence of the bit stability has been determined. The writing threshold power and writing rate have been measured. The results are discussed within the perspective of extension to the nanometer length scale.