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Two water-soluble regioregular poly(3-alkylthiophene)s, incorporating aminic groups at the end of the side chains, have been synthesized using a post-polymerization functionalization procedure on a ω-bromine substituted polyalkylthiophene. The high solubility of the obtained polymers in water allowed for the preparation of “green” bulk heterojunction solar cells which reached a power conversion efficiency of 4.85% when PC 61 BM was used as electron-acceptor material. Improved optical absorption and photocurrent have been obtained by interposing a layer of Ag nanoparticles between the buffer and the photoactive layer, leading to a final power conversion efficiency of 5.51%. [ABSTRACT FROM AUTHOR]

Water-soluble regioregular poly{3-[(6-sodium sulfonate)hexyl]thiophene} (PT6S) and poly{3-[(6-trimethylammoniumbromide)hexyl]thiophene} (PT6N) have been synthesized and employed both as photoactive layers for the assembling of “green” bulk-heterojunction organic solar cells and as charge-collection layers in a cell with “classic” architecture. While the photovoltaic performances obtained with the two aforementioned polymers were lower than the reference cell, their latter use allowed to notably increase the inherent J-V properties, leading to a considerable enhancement in the overall photovoltaic output. The power conversion efficiency of the optimized multilayer BHJ solar cell reached 4.78%, revealing a higher efficiency than the reference cell (3.63%). [ABSTRACT FROM AUTHOR]

Regioregular polyalkylthiophene copolymers were prepared by oxidative copolymerization of known amounts of brominated alkylthiophene monomers possessing or not a reactive bromide group linked at the end of the alkyl chain. Subsequent post-polymerization functionalization with tetraphenylporphyrin led to products with differing dye content in the side chain. Due to their chemical structure, the copolymeric precursors, as well as the porphyrin functionalized derivatives, were fully soluble in common organic solvents and could be used as active layers, in combination with PCBM, for the preparation of polymeric solar cells (PSC) with bulk heterojunction architecture. The power conversion efficiency of the cells containing porphyrin resulted remarkably higher with respect to the cells containing the precursor bromoalkyl moiety in the side chain and one order of magnitude higher with respect to similar previously investigated PSC produced with lower porphyrin content. [ABSTRACT FROM AUTHOR]

A class of eco-friendly copolyesters based on poly(butylene 2,5-thiophenedicarboxylate) (PBTF) is presented. The main goal of the study was to enhance the biodegradation rate of PBTF homopolymer. To this purpose, aliphatic sequences based on adipic acid have been introduced in the macromolecular backbone. The synthesized polymers have been characterized from thermal and structural point of view and their properties have been compared to those of the two homopolymers, i.e. PBTF and poly(butylene adipate). The peculiar microstructure of PBTF, due to the presence of an uninduced 2D-ordered phase, i.e. meso -phase, impacted also the copolymers' behavior, e.g. causing an increase of the materials' stiffness. Biodegradation rate in compost increased with the increase of mobile aliphatic sequences that allowed for an easier access to the ester bonds by the enzymes responsible for chain depolymerization. Lastly, gas permeability resulted strictly dependent on copolymer composition. Copolymers rich in thiophenedicarboxylate co-units displayed a gas barrier behavior comparable to poly(ethylene furanoate), while with the increase of adipate content the permeability increased, remaining however competitive with respect to that of polyolefines and polylactic acid. [ABSTRACT FROM AUTHOR]

New reversible temperature-sensitive polymeric materials with a broad window of trigger temperatures were developed for application as thermal monitoring smart labels for perishable commodities. In particular new liquid crystalline copolymers functionalized with azoaromatic chromophores and chiral cholesteric moieties were synthesized by Controlled Radical Polymerization (CRP) using cheap and easily available reagents and mild reaction conditions. These materials exhibit a chiral nematic phase (N*) with an intense Bragg reflection which gives an iridescent and bright appearance to their thick films. By inducing the azoaromatic trans-cis isomerization through UV irradiation, it is possible to break the native chiral supramolecular conformational order thus leading to an amorphous transparent phase which is characterized by different UV–Vis and CD spectra and which is stable whilst the temperature is kept below the T g of the polymer. Hence, tags can be reused even though the required process is so specific that they cannot be easily tampered. Thus, owing to the high control of the polymer molecular weight and structure allowed by the ATRP technique, it is possible to finely tune the trigger temperature and the photoswitchable properties thus allowing the fabrication of tailor made labels suitable for a huge variety of products with potential applications as sensors and in photonic and display fields. [ABSTRACT FROM AUTHOR]

Abstract: This work investigates the photovoltaic properties of a BHJ solar cell made of an active layer constituted by phenyl-C61-butyric acid methyl ester and a novel polyalkylthiophene derivative functionalized in the side chain with porphyrin dye. The polymer was fully characterized by FT-IR, NMR, UV–vis, GPC, DSC and TGA techniques and the active layer by cyclic voltammetry and AFM. The results of this study indicate that the solar cell made of polythiophene containing a 25% molar content of sensitizer dye as the active layer, exhibits higher power conversion efficiency, short circuit current and fill factor values than the reference cell based on polythiophene completely devoid of porphyrin. [Copyright &y& Elsevier]

Abstract: The electrochemical polymerization of the 3,3″-di[(S)-(+)-2-methylbutyl]-2,2′:5′,2″-terthiophene (DMBTT) monomer was carried out potentiodynamically on indium tin oxide (ITO), Pt or glassy carbon (GC) electrodes in anhydrous CH3CN with TBAPF6 as supporting electrolyte. Films with good adhesion were obtained for all the tested substrates and they were characterized by various analytical techniques including UV–Vis–NIR absorption spectroscopy, cyclic voltammetry (CV), scanning electron microscopy (SEM), and gel permeation chromatography (GPC). The most outstanding properties of the electrochemically synthesized polymer were compared with those of the same polymer obtained by a chemical method. The film obtained on ITO displayed a reversible electrochromic behavior under potential switching between −0.50 and +1.00V vs. SCE. [Copyright &y& Elsevier]

Abstract: Novel optically active methacrylic copolymers, bearing carbazole and azoaromatic moieties linked to the main chain with a rigid (S)-hydroxysuccinimide residue of one prevailing absolute configuration, have been prepared and characterized with the aim to establish the effects of the chiral group and of the dipolar interactions between the two side-chain chromophores on their properties. In particular, the observed chiroptical properties suggest the presence of ordered chiral conformations at least for chain segments of the macromolecules. Spectroscopic, thermal and chiroptical characterizations of these copolymers demonstrate the occurrence of significant electronic interactions between carbazole chromophores and azobenzene moieties. These interactions are related to the unusual partially alternating structure of the investigated copolymers and the relevant chiroptical and thermal properties. In fact, the polymeric derivates show high glass transition temperatures and good thermal stability, thus opening the way to a variety of potential applications based on photoconductive and optoelectronic properties. [Copyright &y& Elsevier]

Abstract: The synthesis of a series of azobenzene containing liquid crystalline methacrylic homopolymers, poly(4-ω-methacryloyloxy-hexyloxy-4′-ethoxyazobenzene) [Poly(M6A)], with distinct average chain lengths and low polydispersity has been achieved by Atom Transfer Radical Polymerization (ATRP) in THF solution using allyl 2-bromoisobutyrate as initiator and Cu(I)Br as catalyst. Under the adopted conditions the living centers concentration is found to be constant throughout the polymerization process and well defined chain end-groups are obtained. All the obtained polymeric samples, having average molecular mass ranging from 3300 to 14000g/mol, exhibit smectic and nematic liquid-crystalline phases on heating, with transition temperatures strongly dependent on polymerization degree, as characterized by differential scanning calorimetry and polarized optical microscopy. The photomechanical effects (i.e. the dependence of volume and density) exhibited upon trans-to-cis and cis-to-trans photoisomerization of the azobenzene mesogenic groups have been investigated by ellipsometry and related to molecular weight, with particular attention to important parameters for potential applications such as the relative variation of total volume, response time, stability and reproducibility. [Copyright &y& Elsevier]

Abstract: Three series of optically active photochromic copolymers, deriving from methyl methacrylate (MMA) and the chiral bisazoaromatic monomers (S)-3-methacryloyloxy-1-[4′-phenylazo-(4-azobenzene)]-pyrrolidine [(S)-MPAAP], (S)-3-methacryloyloxy-1-[4′-cyanophenylazo-(4-azobenzene)]-pyrrolidine [(S)-MPAAP-C] and (S)-3-methacryloyloxy-1-[4′-nitrophenylazo-(4-azobenzene)]-pyrrolidine [(S)-MPAAP-N], have been prepared and characterized in solution and in the solid state with the aim to evaluate the effect on their chiroptical and thermal properties originated by the insertion of inactive MMA groups along the main chain. The optical activity displayed by the bisazo polymers is discussed in terms of extent of chiral conformation assumed by the macromolecules as a consequence of dipole–dipole interactions between the bisazoaromatic chromophores. The photoinduction of birefringence has been assessed on thin films of the investigated copolymers in order to evaluate their behaviour as materials for optical data storage. The results are interpreted in terms of copolymer composition and conformational stiffness of the bisazoaromatic chromophoric co-units, which are responsible for the optical response rates, and are compared to those of the similar derivatives containing only one azo bond. The observed enhanced thermal properties and the temporal stability appear of interest for a potential use of these materials in nano technologies for all-optical data manipulation and in optoelectronics. [Copyright &y& Elsevier]

Abstract: We have investigated a new optically active photochromic homopolymer poly[(R)-3-methacryloyloxy-1-(4′-cyano-4-azobenzene)pyrrolidine] containing in the side-chain a chiral group of one prevailing configuration linked to a trans-azoaromatic system. As expected it exhibits in solution homogeneous conformations with a prevailing chirality induced by dipole–dipole interactions between side-chain chromophores. Copolymers with the enantiomeric monomer (S)-3-methacryloyloxy-1-(4′-cyano-4-azobenzene)pyrrolidine have also been prepared in order to evaluate the effect on the photoinduced optical properties of side-chain chiral groups of opposite configuration in various ratios. The possibility of producing reversible photomodulation of linear birefringence without any significant degradation of these materials seems to be promising for their use in optical data storage. [Copyright &y& Elsevier]

Novel A-B-A triblock copolymers based on poly(l -lactic acid) (PLLA) were designed with an ad hoc chemical structure to prepare micro- and nanoparticles for controlled drug delivery. A block is formed by PLLA, while central B block is a copolymeric system based on poly(butylene succinate) and poly(triethylene succinate): more specifically, two copolymers with fix composition (50:50 mol:mol) and different molecular architecture were synthesized. One of them is characterized by a block architecture, i.e. long butylene succinate and triethylene succinate sequences form the macromolecular chains, the other being on the contrary a random copolymer with short sequences. The so-obtained materials were characterized from the molecular and thermal point of view. Moreover, to investigate the effect of both chemical structure and molecular architecture of the polymers synthesized on drug release kinetics, Dexamethasone-encapsulated micro- and nanoparticles were prepared by oil-in-water miniemulsion technique. These particles were subjected to thermal and morphological characterization. After that, drug release studies were carried out, and the effect of chemical composition, sequence distribution and particle size on release profile was evaluated. • PLLA-based triblock copolymers are obtained by polycondensation and ROP. • Central blocks have different molecular architecture: block and random. • Flexibility, crystallinity degree and wettability depend on molecular architecture. • Dexamethasone-containing micro- and nanoparticles were prepared by miniemulsion. • Drug release can be tuned by varying molecular architecture and particle size. [ABSTRACT FROM AUTHOR]