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 α’-form and the metastable co-crystalline ε-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.     

Polymerization of 3-methyl-1-butene promoted by metallocene catalysts

3-Methyl-1-butene was polymerized in the presence of a number of homogeneous metallocene catalysts (co-catalyst methylalumoxane). Contrary to literature reports, it was found that even the simplest C₂-symmetric metallocenes promote the isotactic polymerization of this monomer with reasonable productivities. Quite surprisingly, a prevailingly isotactic polymer was also obtained in the presence of C_s-symmetric metallocenes, which are instead syndiotactic-specific in propene polymerization.     

Thermal Plasma Synthesis of Zirconia Powder and Preparation of Premixed Ca-Doped Zirconia

A novel study about the synthesis of zirconia and calcia-stabilized zirconia powders were carried out by DC thermal plasma starting from cheap precursors as the carbonates. Different operational parameters were investigated to explore the effects of the process conditions, such as the plasma torch power and the gas flow rate on the composition and the morphology of the powders. The products phase changes from a metastable tetragonal to monoclinic/tetragonal mixture. Basically a main tetragonal phase was obtained at low torch power (7 kW) while the amount of monoclinic phase linearly rises with the power, up to 66 wt% at 26 kW of plasma power and high gas flow rate. The gas flow rate also affects the shape and the size of the powder, where high values reduce powder aggregation and enhance the spherical shape. The best results were achieved at 22 kW of plasma power and high gas flow rate, with powders of roundness about 79% and a wide particle size distribution. Adding the calcium carbonate to the zirconium carbonate (corresponding to 8 wt% CaO in the final mixture), the plasma treatment mainly produces a tetragonal phase zirconia, that at 1400 °C in furnace changes in a stable cubic phase. These powders could be made suitable for further industrial applications after proper treatments.

     

Selective surface modification of syndiotactic polystyrene films: A study by Fourier transform- and confocal-Raman spectroscopy

A helical crystalline modification of syndiotactic polystyrene (sPS), the δ-form, was employed to prepare solution-cast films selectively sulfonated on the surface. This result was achieved because of the unusual transport characteristics of the δ-form, exhibiting comparatively large diffusivity and solubility values for low-molecular weight compounds such as chloroform, which can be effectively used as a carrier solvent. The results of sulfonation of the δ-form are compared with those obtained with a trans-planar crystalline modification of sPS (β-form). The latter was found unsuitable for selective surface modification. The analysis of the sulfonated films was carried out by FT-Raman and confocal-Raman spectroscopy. The first technique was used to investigate the average composition of the samples in terms of sulfonation degree and crystalline structure. It also allowed us to construct calibration curves to be used in connection with the confocal-Raman data. The latter technique was employed to generate images with spectroscopic contrast and to quantitatively characterize the depth-profiles of the investigated films.     

Influence of fillers concentration on electrical properties of polystyrene matrix doped by gold nanoparticles and 8HQ

The analysis of the electrical properties of polystyrene films containing gold nanoparticles capped with 1-dodecanethiol and 8-hydroxyquinoline molecules is reported. The conductivity of the nanocomposite as a function of the doping level has been investigated both in planar and stacked configurations. While the former configuration evidenced low field tunneling between nanoparticles in the polymer matrix, stacked devices allowed us to investigate the main phenomena ruling the transport properties when switching effects are present close to critical electric fields. In particular, through the analysis of current-voltage characteristics we studied the charge transport at different fillers concentrations and sketched a physical picture of conductivity in such nanocomposite systems.     

Regiospecificity of 1-butene polymerization catalyzed by C2-symmetric group IV metallocenes

The regiospecificity of isotactic 1-butene polymerization promoted by typical C₂-symmetric group IV metallocene catalysts was studied by means of ¹³C NMR spectroscopy. In particular, the formation of 1,4 monomer enchainments is discussed.     

Polyelectrolyte Membranes Based on Sulfonated Syndiotactic Polystyrene in Its Clathrate Form

Recently, more and more attention has been focused on new techniques for energy production also in view of environmental problems. A noticeable device is small fuel cell that converts chemical energy into electric energy by electrochemical reaction of hydrogen with oxygen, and exhibits a high-energy efficiency. Conventional small fuel cells have been classified into phosphoric acid-type fuel cells, molten carbonate-type fuel cells, solid oxide-type fuel cells, solid polymer type fuel cells, etc., according to the type of electrolyte used. The target of this work is the development of a new process to build up polyelectrolyte membranes, for polymer type fuel cell (PEM), by sulfonating syndiotactic polystyrene in its clathrate form. The polyelectrolyte membranes of this paper are inexpensive and exhibit good long-term stability and ion exchange capability.