Electrochemical Characterization and CO2 Reduction Reaction of a Family of Pyridazine-Bridged Dinuclear Mn(I) Carbonyl Complexes.

Three recently synthesized neutral dinuclear carbonyl manganese complexes with the pyridazine bridging ligand, of general formula [Mn2(µ-ER)2(CO)6(µ-pydz)] (pydz = pyridazine; E = O or S; R = methyl or phenyl), have been investigated by cyclic voltammetry in dimethylformamide and acetonitrile both under an inert argon atmosphere and in the presence of carbon dioxide. This family of Mn(I) compounds behaves interestingly at negative potentials in the presence of CO2. Based on this behavior, which is herein discussed, a rather efficient catalytic mechanism for the CO2 reduction reaction toward the generation of CO has been hypothesized.

New Sustainable Multilayered Membranes Based on ZrVTi for Hydrogen Purification.

Some metals belonging to groups IV and V show a high permeability to hydrogen and have been studied as possible alternatives to palladium in membranes for hydrogen purification/separation in order to increase their sustainability and decrease their costs. However, to date, very few alloys among those metals have been investigated, and no membrane studies based on 4-5 element alloys with low or zero Pd content and quasi-amorphous structure have been reported so far. In this work, new membranes based on ZrVTi- and ZrVTiPd alloys were tested for the first time for this application. The unprecedented deposition of micrometric-based multilayers was performed via high-power impulse magnetron sputtering onto porous alumina substrates. Dense Pd/ZrxVyTizPdw/Pd multilayers were obtained. The composition of the alloys, morphology and structure, hydrogen permeance, selectivity, and resistance to embrittlement were tested and analyzed depending on the deposition conditions, and the membrane with the enhanced performance was tuned. The environmental impact of these membranes was also investigated to ascertain the sustainability of these alloys relative to more common Pd77Ag23 and V93Pd7 thin-film membranes using a life cycle assessment analysis. The results showed that the partial substitution of Pd can efficiently lead to a decrease in the environmental impacts of the membranes.

Distribution in the brain and possible neuroprotective effects of intranasally delivered multi-walled carbon nanotubes.

Carbon nanotubes (CNTs) are currently under active investigation for their use in several biomedical applications, especially in neurological diseases and nervous system injury due to their electrochemical properties. Nowadays, no CNT-based therapeutic products for internal use appear to be close to the market, due to the still limited knowledge on their fate after delivery to living organisms and, in particular, on their toxicological profile. The purpose of the present work was to address the distribution in the brain parenchyma of two intranasally delivered MWCNTs (MWCNTs 1 and a-MWCNTs 2), different from each other, the first being non electroconductive while the second results in being electroconductive. After intranasal delivery, the presence of CNTs was investigated in several brain areas, discriminating the specific cell types involved in the CNT uptake. We also aimed to verify the neuroprotective potential of the two types of CNTs, delivering them in rats affected by early diabetic encephalopathy and analysing the modulation of nerve growth factor metabolism and the effects of CNTs on the neuronal and glial phenotypes. Our findings showed that both CNT types, when intranasally delivered, reached numerous brain areas and, in particular, the limbic area that plays a crucial role in the development and progression of major neurodegenerative diseases. Furthermore, we demonstrated that electroconductive MWCNTs were able to exert neuroprotective effects through the modulation of a key neurotrophic factor and probably the improvement of neurodegeneration-related gliosis.

Thermally Induced Synthesis of Anthracene-, Pyrene- and Naphthalene-Fused Porphyrins.

The synthesis of π-extended porphyrins containing anthracenyl moieties still represents an important challenge. Here, we report on the synthesis of a series of unsubstituted naphthyl-, pyrenyl- and anthracenyl-fused zinc porphyrin derivatives. To this aim, meso-substitued porphyrins are synthesized and the fusion of the PAHs (Polycyclic Aromatic Hydrocarbon) on the ß-positions are performed through thermally induced dehydro-aromatization. The fused zinc-porphyrin derivatives are fully characterized and their optical absorption and photoluminescence properties are reported. We also demonstrate that zinc can be removed from the porphyrin core, giving rise to pure C, H, N materials. This work constitutes the first step towards the synthesis of the fully-fused tetra-anthracenylporphyrin.