Spectral imaging method for studying Physarum polycephalum growth on polyaniline surface.

The features of spectrophotometric scanner, generally exploited in the artwork field, are here considered in a non-conventional context to characterize the networks created by Physarum polycephalum slime mold during its motion on glass substrates covered with polyaniline: a polymer that varies its color and conductive properties according to the redox state. The used technique allowed the investigation of the effects coming out from the interaction between P. polycephalum and polyaniline. Thus, the contactless method of the analysis of polyaniline conductivity state resulted from the slime mold metabolism was suggested. Indeed, it is here demonstrated that P. polycephalum can modify properties of polyaniline due to its internal activity in contact zones.

A hybrid living/organic electrochemical transistor based on the Physarum polycephalum cell endowed with both sensing and memristive properties.

A hybrid bio-organic electrochemical transistor was developed by interfacing an organic semiconductor, poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonate), with the Physarum polycephalum cell. The system shows unprecedented performances since it could be operated both as a transistor, in a three-terminal configuration, and as a memristive device in a two terminal configuration mode. This is quite a remarkable achievement since, in the transistor mode, it can be used as a very sensitive bio-sensor directly monitoring biochemical processes occurring in the cell, while, as a memristive device, it represents one of the very first examples of a bio-hybrid system demonstrating such a property. Our system combines memory and sensing in the same system, possibly interfacing unconventional computing. The system was studied by a full electrical characterization using a series of different gate electrodes, namely made of Ag, Au and Pt, which typically show different operation modes in organic electrochemical transistors. Our experiment demonstrates that a remarkable sensing capability could potentially be implemented. We envisage that this system could be classified as a Bio-Organic Sensing/Memristive Device (BOSMD), where the dual functionality allows merging of the sensing and memory properties, paving the way to new and unexplored opportunities in bioelectronics.

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.

Doping-induced conductivity transitions in molecular layers of polyaniline: detailed structural study.

We report detailed structural investigations, by synchrotron X-ray reflectivity (XRR), grazing incidence diffraction (GID), and space-resolved grazing incidence X-ray-induced fluorescence (GIXF), on the structure of molecular layers of polyaniline (PANI) that can be converted from insulating to conducting state simply by doping. We first address the simpler, but more intriguing, system, i.e., a floating monolayer of PANI on different subphases, for which we found a typical thickness of 28(1) A, not much affected by the doping process. For the doped film we also found an internal lateral structure, with in-plane spacing of 3.5 A-albeit with a small coherence of 3-4 repeat units only-compatible with face-to-face interchain stacking of phenyl rings, in agreement with the literature. By GIXF we could confirm the crucial role of Cl(-) intercalation in the doping process of the PANI film: under doping conditions (0.1 M HCl subphase) the Cl(-) intake is 8 times larger than in nondoping conditions (0.1 M KCl subphase). Multilayers transferred onto solid substrate were studied also as a function of the applied voltage, as this system constitutes the core of an electrochemically controlled device whose strongly nonlinear characteristic make it useful for applications to adaptive networks for complex information processing. By the application of an electrostatic field of 140 V/m, Cl ionic migration was observed confined to the polymeric film surface.

Sorption of amines by the Langmuir-Blodgett films of soluble cobalt phthalocyanines: evidence for the supramolecular mechanisms.

By means of microgravimetry, UV-Vis spectroscopy and optic microscopy, sorption of pyridine, primary aliphatic amines and benzylamine by the Langmuir-Blodgett (LB) films of tetra-4-tert-butyl- and tetra-(3-nitro-5-tert-butyl)-substituted cobalt phthalocyanines (CoPc' and CoPc*, respectively) was studied over a broad concentration range. In general, sorption occurs as stepwise intercalation of the sorbate molecules into the supramolecular 3D structure of the phthalocyanine assembly followed by formation of the donor-acceptor complexes. Both intercalation depth and stoichiometry of the complexes are determined by the molecular structure of amines. The supramolecular factor allows discrimination between amines in air but not in aqueous solutions because of concurrent intercalation of water.

Molecular relaxation and microscopic structure of multilayers and superlattices of a photosensitive liquid-crystalline polymer.

We report a detailed study of photoinduced changes in the microscopic structure of monolayers, multilayers, and superlattices of a photosensitive side chain liquid crystalline polymer, deposited by the Langmuir-Schaefer technique. We probe both out-of-plane and in-plane ordering and its changes due to optical pumping of the trans-cis photoisomerization transition of the azobenzene side chain in an azopolyacrylate. Microscopic structure was studied mainly by synchrotron radiation x-ray reflectometry and grazing incidence diffraction; we also used null-ellipsometry and atomic force microscopy. Our results provide a quantitative modeling of the structural changes and corresponding relaxation times taking place as a function of confinement, temperature and optical pumping, and in particular confirm previously reported ellipsometric results on such changes as a function of sample thickness. This allows a quantitative description of the effects of reduced dimensionality on the structural transitions in this glass-forming system.

Qualitative and quantitative analysis of the secondary structure of cytochrome C Langmuir-Blodgett films.

A qualitative and quantitative analysis of the conformation of Langmuir-Blodgett (LB) dried films of cytochrome C on silicon wafers was performed by Fourier transform ir (FTIR) spectroscopy. A deconvolution procedure was applied to the amide I band analysis, in order to determine the percentage of the different secondary structures. Qualitative analysis was performed by examining difference spectra. Films obtained by spreading protein solutions at pH 7.4 and 1, dried at 25 and 100 degrees C, on silicon wafers were also examined in order to detect spectral components associated with denatured protein domains, and to compare them with cytochrome C LB films. FTIR spectroscopy showed that the following important changes characterise LB film spectra: (a) the alpha-helix component is higher (its percentage is 57 and 54%) than the one estimated in dried film obtained by spreading the solutions at pH 7.4 on a silicon substrate (43%), (b) there is an increase in the intensity of bands attributed to protonated carboxy group bands, involved and not involved in the formation of hydrogen bonds, and a decrease in those attributed to deprotonated carboxy groups, (c) the intensity of several bands attributed to aromatic amino acids and aliphatic chains increases, and (d) bands due to O-H stretching vibrations of crystallization water are present. These conformational changes could be induced by protein-protein interaction caused by the close packing of molecules that occurs during LB film formation; it cannot be excluded that they may be accompanied by partial changes in the tertiary structure of the protein. A preferential orientation of protein molecules in LB films is also a possibility.