A new polythiophene derivative bearing an azobenzene substituent at the end of a ethylenic side-chain was synthesized and characterized by FT-IR spectroscopy, H-1 and C-13 NMR spectroscopy, DSC, TGA, XRD, and UV-vis spectroscopy. Its electrical conductivity was measured and its second-order NLO activity was by SHG. Structure-property relations were elucidated by comparison with a similar polymer only partially substituted by the NLO-active chromophore. The molecular design of the chromophoric system allows high and stable non-linear coefficients d(33) to be obtained, making these polymers suitable for the construction of second-harmonic generators with improved efficiency and life-time.

The solvatochromic behaviour of different functional group-bearing and self-interacting polyalkylthiophenes with strong chromic responses in solution and self-assembling capacity in the solid state is investigated here. The menagerie of species deriving from the conformational freedom of the conjugated chains in solution has been examined in different solvent mixtures as their physico-chemical nature sensibly affects final material morphology in the solid (film) state. Memory of solution curling shape and of the degree of aggregation is in fact retained through casting or spin-coating procedures and permanently endures in the polymeric film. The efficiency of the final device based on the ICP (inherent conducting polymer) film may therefore be improved by simply acting on its morphology, which is directly determined by polymer dissolution conditions.

The synthesis of new regioregular polyalkylthiophenes derivatives with different substituents inserted in the terminal position of a hexamethylenic side chain is described here. The new polymers were prepared by simple and effective post-polymerization functionalization of a soluble regioregular precursor, namely poly[3-(6-bromohexyl)thiophene] that was obtained by regiospecific organometallic coupling. The new materials were characterized by NMR, FT-IR, elemental analysis and their molecular weights determined by gel permeation chromatography. High-precision UV–Vis analyses (solvatochromism and affinitychromism) were conducted in solution and in film state, and the results are discussed in relation to the different inserted functional groups. Thanks to the good sensitivity and chromic response recorded for the prepared materials to different analytes and in some solvating systems, they appear to have great potential for use as electronic sensors in chemo-recognition applications.

Electrochemical polymerization of thiophene oligomers (n = 4) bearing an hexamethylenic ω-methoxy functionalized side chain at the 3-3″′ position of the thiophene rings, was performed in different solvents and electrode surfaces. The degree of polymerization and the electrochemical behaviour of the different electrosynthetized polymers were compared with a polymer obtained by a chemical method. The polymeric films were characterized using cyclic voltammetry, FT-IR, AFM and SEM microscopy.

Regioregular azobenzene-substituted polythiophenic copolymers were prepared by a regiospecific organometallic polycondensation procedure based on a Grignard metathesis reaction. Copolymers with a high content of chromophoric groups in the side chains and a high degree of configurational order of the backbones were obtained. A sample was also functionalized with hydroxyalkyl chains capable of setting up ordered supramolecular structures through hydrogen bonds. The final materials were fully characterized via NMR, IR, elemental analysis, GPC, DSC and X-ray diffraction. Moreover, measurements of NLO activity on polymer films showed the synthetic strategies adopted and monomers used to be correct. Values obtained by the in situ deprotection of the interacting functional groups after the alignment of the chromophorized side chains were very promising, proving the procedure to be suitable for industrial and commercial applications.

A new poly(3-alkyl)thiophene bearing a piperidinic moiety in the side chain was synthesized in different ways with satisfactory yields in soluble fractions at high molecular weights. The chromic behaviors of the different polymeric samples were studied by UV–vis spectroscopy in different solvent/non-solvent mixtures and in the presence of some analytes; a strong affinitychromism toward bicarboxylic acids was observed. The good chromic response and its independence from the structural parameters of the polymer indicate the development of a very useful and easily obtainable colorimetric tool for the quick, sensitive and selective detection of diacid molecules in organic solvents.

A series of newly ester-substituted polyalkylthiophenes (PATEs) was prepared. All polymers were fully soluble in common organic solvents, which allowed for a wide range of physico-chemical measurements, including solvato- and thermo-chromic, thermal, microstructural and electrical (in neutral and doped state) analyses. Marked differences were observed in the material characteristics of these polyalkylthiophene derivatives. It was thus possible to identify and describe the different properties ascribable not only to the different esteric groups in side chain but also to the different average degrees of functionalization of the thiophenic repeating units. In neutral state the PATEs of this study proved to be thermostable and soluble, while at the same time exhibiting high ordered molecular assemblies leading to high average conjugation lengths, electrical conductivities and stabilities. These polymers can also be easily and quantitatively transformed in other PAT derivatives using simple nucleophilic reactions either in solution or in solid (film) state. In view of the above and given that these polymers can be profitably and inexpensively synthesized, their future use for innovative applications in the field of synthetic metals appears feasible as from now.

The UV-vis spectral profiles of some alkylthiophene copolymers in CHCl3 solutions, variously substituted with an azobenzenic NLO chromophore have been carefully analyzed and distinct intensity contributions have been assigned to the overlapped electronic transitions appearing in the lower energy part of the spectra. The different spectral behaviours are influenced by the chromophore content, the length of the alkylic side-chain of the plastifying comonomer and, more significantly, by the number of the carbon atoms in the oligomethylenic spacer between the chromophoric group and the conjugated polythiophenic chain. This latter finding can be correlated with the strong steric hindrance caused by chromophore crowding in close proximity to the polymeric backbone. As the intensity distributions may be reasonably compared with the NLO properties, identification of the above parameters and of their role is an important step towards the synthesis of polyalkylthiophenes with predictable electronic properties and the development of materials with enhanced NLO characteristics.

A novel series of functionalized polythiophenes incorporating 3-(ω-bromoalkyl) pendants are synthesized by electrochemical polymerization. The effect of the solvent on the electrosynthesis is investigated. The polymeric films are characterized using cyclic voltammetry, FT-IR, AFM and SEM microscopy. The poly[3-(6-bromohexyl)thiophene] film cast on GC or ITO electrode surface is compared with a sample obtained by a chemical method.

The preparation of a new thiophenic dimer partially derivatized with a bromohexylic chain is described. its polymerization under mild oxidative conditions leads to a polythiophene with a degree of functionalization Of 50% and highly soluble in organic solvents. The product has been fully characterized by FT-IR, H-1 and C-13 NMR using one and two-dimensional techniques as well as by SEC and thermal analysis. Solvatochromic effects of the new polymer have been investigated in different mixtures, underlining its self-assembling capability even in solvated states.

As described at previous ASME-PVP Conferences, large efforts have been devoted by the Italian Agency for New Technology, Energy and the Environment (ENEA), with the cooperation of several further members of the Italian Working Group on Seismic Isolation (GLIS), to the development, validation and application of innovative anti-seismic (IAS) techniques since 1988. Considered have been base and floor seismic isolation systems, energy dissipation systems consisting of various types of passive devices (elastic-plastic, viscous, visco-elastic and electro-inductive dampers), hydraulic coupling systems using innovative shock transmitters, systems formed by shape memory alloy devices and more recently, semi-active control systems of vibrations. New activities at ENEA, which are in progress in the framework of both international and national collaborations, concern the development of new IAS systems of the aforesaid kinds to be applied to: • civil structures (bridges, viaducts and buildings of various types) and industrial plants, in both cases to be constructed or seismically retrofitted; • cultural heritage to be restored or reconstructed, or masterpieces to be seismically protected. This paper focuses on the progress of the studies concerning the first kind of structures (SPIDER, SPACE, ALGA-DECS and ISI Projects), while that for cultural heritage has been dealt with in a separate paper presented at this Conference. In addition, some new projects involving ENEA, which were recently proposed to the European Commission and Italian Ministry for the Environment, are mentioned. The ENEA activities being performed for the above-mentioned projects take advantage of the collaboration of the Universities of Bologna and Ancona and “Studio Antonucci” consulting office. The most recent results of the numerical and experimental studies confirm the adequacy and benefits of the proposed systems for the construction or retrofit the various types of considered structures. Finally, it is worthwhile stressing that two further separate papers presented at this Conference deal with the main features and results of the 7th International Seminar on Seismic Isolation, Passive Energy Dissipation and Active Control of Vibrations of Structures (Assisi, Italy, October 2–5, 2001), which was organized by GLIS with the support of ENEA, and the series of films on the IAS techniques which have been produced in the framework of the MUSICA Project.