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The stereoselective polymerization of conjugated dienes promoted by using transition metal complexes has attracted much interest in both industrial and academic environments for the relevance of polydienes as synthetic rubbers and for the challenging reaction mechanisms. Among the different transition metal complexes, those based on group IV have been demonstrated to be versatile and efficient catalysts. Titanium complexes are generally more active than zirconium complexes. A rare exception to this trend is represented by a series of Zr(IV) complexes supported by (anilidomethyl)pyridine ligands that, after activation by using Al(iBu2H)/MAO, were found to be highly active affording exclusively cis-1,4-polybutadiene. To rationalize this unexpected trend and to obtain more insights into the parameters that control the reactivity of group IV complexes, a theoretical investigation of the entire polymerization mechanism, employing density functional methods, was undertaken. In the framework of the widely accepted polymerization scheme, the different intermediates featuring h4 (both cis and trans) coordination of the monomer and h1 or h3 (syn or anti)allyl coordination of the growing chain were scrutinized. Subsequently, the effects of the metal center on the free-energy profiles of the elementary steps involved in the reaction were examined. The results presented herein aim to achieve a better knowledge of the influence of the metal on the polymerization rates and on the stereoselectivity of the reaction.

In this work, two compounds belonging to the BODIPY family, and previously investigated for their photosensitizing properties, have been bound to the amino-pendant groups of three random copolymers, with different amounts of methyl methacrylate (MMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) in the backbone. The P(MMA-ran-DMAEMA) copolymers have inherently bactericidal activity, due to the amino groups of DMAEMA and to the quaternized nitrogens bounded to BODIPY. Systems consisting of filter paper discs coated with copolymers conjugated to BODIPY were tested on two model microorganisms, Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). On solid medium, irradiation with green light induced an antimicrobial effect, visible as a clear inhibition area around the coated disks. The system based on the copolymer with 43% DMAEMA and circa 0.70 wt/wt% of BODIPY was the most efficient in both bacterial species, and a selectivity for the Gram-positive model was observed, independently of the conjugated BODIPY. A residual antimicrobial activity was also observed after dark incubation, attributed to the inherently bactericidal properties of copolymers.

N-doped TiO2 (N-TiO2) and N-doped ZnO (N-ZnO) were synthesized utilizing ammonia as a dopant source. The chemico-physical characteristics of synthesized samples were studied by Raman spectroscopy, X-ray diffraction, SEM analysis, N2 adsorption–desorption at −196 °C, and diffuse reflectance spectroscopy. Compared to undoped samples, the introduction of nitrogen in the semiconductor lattice resulted in a shift of band-gap energy to a lower value: 3.0 eV for N-ZnO and 2.35 eV for N-TiO2. The photocatalysts were tested for the degradation of Eriochrome Black T (EBT), which was selected as a model azo dye. Both N-doped semiconductors evidenced an improvement in photocatalytic activity under visible light irradiation (62% and 20% EBT discoloration for N-TiO2 and N-ZnO, respectively) in comparison with the undoped samples, which were inactive in the presence of visible light. Different behavior was observed under UV irradiation. Whereas N-TiO2 was more photoactive than commercial undoped TiO2, the introduction of nitrogen in ZnO wurtzite resulted in a drastic reduction in photocatalytic activity, with only 45% EBT discoloration compared to total color removal obtained with the commercial ZnO sample, suggesting intrinsic limitations for doping of this class of semiconductors.

The last decades have witnessed a rapid growth of applications of N-heterocyclic carbenes (NHCs) in different chemistry fields. Due to their unique steric and electronic properties, NHCs have become a powerful tool in coordination chemistry, allowing the preparation of stable metal-ligand frameworks with both main group metals and transition metals. An overview on the use of five membered monodentate C2-symmetric N-heterocyclic carbenes (NHCs) as ligands for transition-metal complexes and their most relevant applications in asymmetric catalysis is offered.

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.

Different tri-doped TiO2 photocatalysts (Fe-N-P/TiO2, Fe-N-S/TiO2, Fe-Pr-N/TiO2, Pr-N-S/TiO2, and P-N-S/TiO2) were successfully prepared and tested in the photocatalytic removal of thiacloprid (THI) under UV-A, visible, and direct solar light irradiation. The physical-chemical properties of the prepared catalysts were analyzed by different characterization techniques, revealing that dopants are effectively incorporated into the anatase TiO2 lattice, resulting in a decrease of the energy band gap. The reduction of photoluminescence intensity indicates a lower combination rate and longer lifespan of photogenerated carriers of all doped samples in comparison with the un-doped TiO2. The doped photocatalysts not only significantly promote the photodegradation under UV-A light irradiation but also extend the optical response of TiO2 to visible light region, and consequently improve the visible light degradation of THI. Fe-N-P tri-doped TiO2 sample exhibits the highest THI photodegradation degree (64% under UV-A light, 29% under visible light and 73% under solar light).

Polypropylene oxide (PPO) and poly(9-(2,3-epoxypropyl) carbazole) (PEPK) di-block copolymers are prepared in one pot via sequential monomer addition by using i-PrONa/i-Bu3Al as an anionic catalytic system. An almost 100% monomer conversion is obtained, and the length of each block is controlled through the monomer/catalyst ratio used. Copolymer molecular weights are quite close to theoretical values calculated assuming the formation of one polymer chain per catalyst; therefore, it is hypothesized that the polymerization reaction proceeds with a living character. The synthesis appears to be particularly efficient and versatile. The calorimetric properties of copolymers obtained in this work are remarkable, since they show two distinct Tg values, corresponding to the PPO and PEPK blocks. The optical measurements of di-block copolymers show more analogous features than those of PEPK homopolymer. Copolymer solution emission spectra just exhibit isolated carbazole fluorescence, whereas in the solid state, film spectra show excimer fluorescence.