Highly Isotactic Poly(N-butenyl-carbazole): Synthesis, Characterization, and Optical Properties

The synthesis of isotactic poly(N-butenyl-carbazole) (i-PBK) by using homogeneous isospecific Ziegler-Natta catalytic system is reported. The achieved polymer is crystalline and shows, to DSC and X-ray analysis, two distinct crystalline phases.i-PBK FTIR spectrum and X-ray diffraction pattern are compared with those of poly(N-vinylcarbazole) (PVK). The observed differences are tentatively associated with higher flexibility of thei-PBK chains due to the alkylene group connecting the carbazole group to the main chain.i-PBK optical properties are also compared with those of PVK and isotactic poly(N-pentenyl-carbazole) (i-PPK), a higher homologue ofi-PBK recently used as emitting layer in organic light emitting diodes (OLEDs) showing white light emission. The close similarity of the fluorescence spectra ofi-PBK andi-PPK is a promising basis for optical applications of this polymer

Crystal structure of the stereoregular ethylene-alt-styrene copolymer synthesized with a zirconocene-based catalyst

A stereoregular alternating ethylene-styrene copolymer, also stretchable in fiber form, has been obtained with rac-isopropylidenebis( l-indenyl)zirconium dimethyldiamide activated by the methylalumoxane catalytic system. From X-ray diffraction fiber spectra, an isotactic structure has been assigned to this copolymer as well as the previously described stereoregular ethylene-styrene copolymers. The polymer has zigzag planar chain conformation with phenyl groups oriented perpendicularly to the chain axis. The crystallographic symmetry in B2/m. Lattice constants (monoclinic, unique axis c): a = 10.23, b = 15.53, c = 5.12 Angstrom; gamma = 98.6 degrees. The disagreement index for measured reflections is R-1 = 0.10

Potential contact and intraocular lenses based on hydrophilic/hydrophobic sulfonated syndiotactic polystyrene membranes

Abstract Crystalline films of syndiotactic polystyrene (s-PS), a commercially available thermoplastic polymer, having a highly hydrophilic amorphous phase, were achieved by using a mild solid-state sulfonation procedure. Despite the used mild process conditions, an easy and uniform sulfonation of the phenyl rings of the amorphous phase is obtained. The crystallinity of the polymer was not affect by the sulfonation degree (S), at least at S less than 20%, and the obtained polymer films show the nanoporous crystalline form of s-PS. As widely reported in literature, the nanoporous nature of the polymer crystalline phase gives to these materials the ability to absorb and release organic molecules of appropriate size and polarity. This property, coupled to transparency, makes these materials potentially useful intraocular lens (IOLs) and contact lens applications. Sulfonation procedure and sulfonated film samples characterization by using wide-angle X-ray diffraction (WAXD), Fourier-transform infrared (FTIR) and ultraviolet-visible (UV-vis) spectroscopy techniques and water sorption tests were reported. Furthermore, the biocompatibility study demonstrated no cytotoxicity and appropriate cell interaction properties for the specific applications

Selective Oxidation of Benzene to Phenol using Fe-N-codoped TiO2 Embedded in Monolithic Syndiotactic Polystyrene Aerogel

A polymeric composite consisting of Fe-N-codoped TiO2 (Fe-N-TiO2) dispersed into a monolithic syndiotactic polystyrene (sPS) aerogel (Fe-N-TiO2/sPS, 10/90 w/w) was used for the photocatalytic hydroxylation of benzene to phenol in presence of H2O2 to enhance the phenol selectivity and yield compared to Fe-N-TiO2 in powder form. Under UV light, Fe-N-TiO2/sPS composite aerogel showed selectivity to phenol of 43%, one order of magnitude more than the selectivity showed by Fe-N-TiO2 in powder form (4%). Under visible light irradiation Fe-N-TiO2 in powder form did not produce phenol, whereas selectivity to phenol of Fe-N-TiO2/sPS was 16%. The polymeric composite was recycled and reused up to five times without a significant decrease in photocatalytic oxidation activity in terms of benzene conversion and phenol yield, indicating the stability of the catalytic composite. Therefore, it was proved that the obtained photoreactive polymer composite could allow the development of innovative sustainable processes able to realize the selective oxidation reactions of aromatic hydrocarbons under mild conditions

Polydopamine-Coated Poly-Lactic Acid Aerogels as Scaffolds for Tissue Engineering Applications

Poly-L-lactic acid (PLLA) aerogel-based scaffolds were obtained from physical PLLA gels containing cyclopentanone (CPO) or methyl benzoate (BzOMe) molecules. An innovative single step method of solvent extraction, using supercritical CO2, was used to achieve cylindrical monolithic aerogels. The pore distribution and size, analyzed by SEM microscopy, were found to be related to the crystalline forms present in the physical nodes that hold the gels together, the stable alpha'-form and the metastable co-crystalline epsilon-form, detected in the PLLA/BzOMe and PLLA/CPO aerogels, respectively. A higher mechanical compressive strength was found for the PLLA/CPO aerogels, which exhibit a more homogenous porosity. In vitro biocompatibility tests also indicated that monolithic PLLA/CPO aerogels exhibited greater cell viability than PLLA/BzOMe aerogels. An improved biocompatibility of PLLA/CPO monolithic aerogels was finally observed by coating the surface of the aerogels with polydopamine (PDA) obtained by the in situ polymerization of dopamine (DA). The synergistic effect of biodegradable polyester (PLLA) and the biomimetic interface (PDA) makes this new 3D porous scaffold, with porosity and mechanical properties that are tunable based on the solvent used in the preparation process, attractive for tissue engineering applications

Molecular Sensing by Nanoporous Crystalline Polymers

Chemical sensors are generally based on the integration of suitable sensitive layers and transducing mechanisms. Although inorganic porous materials can be effective, there is significant interest in the use of polymeric materials because of their easy fabrication process, lower costs and mechanical flexibility. However, porous polymeric absorbents are generally amorphous and hence present poor molecular selectivity and undesired changes of mechanical properties as a consequence of large analyte uptake. In this contribution the structure, properties and some possible applications of sensing polymeric films based on nanoporous crystalline phases, which exhibit all identical nanopores, will be reviewed. The main advantages of crystalline nanoporous polymeric materials with respect to their amorphous counterparts are, besides a higher selectivity, the ability to maintain their physical state as well as geometry, even after large guest uptake (up to 10–15 wt%), and the possibility to control guest diffusivity by controlling the orientation of the host polymeric crystalline phase. The final section of the review also describes the ability of suitable polymeric films to act as chirality sensors, i.e., to sense and memorize the presence of non-racemic volatile organic compounds

Stereoselective Ring-Opening (Co)polymerization of β-Butyrolactone and ε-Decalactone Using an Yttrium Bis(phenolate) Catalytic System

An effective route for ring-opening copolymerization of β-butyrolactone (BBL) with ε-decalactone (ε-DL) is reported. Microstructures of the block copolymers characterized by 13C NMR spectroscopy revealed syndiotactic-enriched poly(3-hydroxybutyrate) (PHB) blocks. Several di- and triblock copolymers (PDL-b-PHB and PDL-b-PHB-b-PDL, respectively) were successfully synthesized by sequential addition of the monomers using (salan)Y(III) complexes as catalysts. The results from MALDI-ToF mass spectrometry confirmed the presence of the copolymers. Moreover, thermal properties of the block copolymers were also investigated and showed that the microphase separation of PDL-b-PHB copolymers into PHB- and PDL-rich domains has an impact on the glass transition temperatures of both blocks