Danilo Malferrari

Introduction of oxygenated side chain into imidazolium ionic liquids: Evaluation of the effects at different biological organization levels

The biological effects of a class of oxygenated imidazolium ionic liquids were studied in comparison with alkyl imidazolium salts (BMIM BF4 and BMIM N(CN)2).The cellular and subcellular effects were evaluated on rat pheochromocytoma PC12 cell lines, through MTT test, lactate dehydrogenase release and acetylcholinesterase inhibition; the eco-toxicological responses were assessed through the acute toxicity tests towards Daphnia magna and Vibrio fischeri. The introduction of ethoxy moieties in the lateral chain of imidazolium cations reduced the biological effects in all the tests. The acute toxicity towards D. magna was not affected by the number of ethoxy units, but the crustacean seemed to be sensitive to the type of anion; on the contrary, a further addition of ethoxy moieties increased the toxicity towards V. fischeri, M(OE)4MIM N(CN)2 being the most toxic oxygenated ionic liquid. In the cytotoxicity assays the salts with oxygenated cations resulted ineffective compared to BMIMs, independently from the anion and the number of ethoxy units in the lateral chain. In order to estimate the influence on membrane fluidity, an analysis of fluorescence anisotropy was done and it indicated that BMIM BF4, the most toxic ionic liquid among the tested ones, led to a destabilization of the model membranes at any molarity.

Poly(methyl methacrylate)-Supported Polydiacetylene Films: Unique Chromatic Transitions and Molecular Sensing

Polydiacetylenes (PDAs) constitute a family of conjugated polymers exhibiting unique colorimetric and fluorescence transitions, and have attracted significant interest as chemo- and biosensing materials. We spin-coated PDA films upon poly(methyl methacrylate) (PMMA), and investigated the photophysical properties and sensing applications of the new PDA configuration. Specifically, the as-polymerized blue PDA layer underwent distinct transformations to purple, red, and yellow phases, which could be quantified through conventional color scanning combined with application of image analysis algorithms. Furthermore, we recorded a reversible red-purple PDA transition that was induced by ultraviolet irradiation, a phenomenon that had not been reported previously in PDA film systems. We show that distinct color and fluorescence transitions were induced in the PMMA-supported PDA films by amphiphilic substances-surfactants and ionic liquids-and that the chromatic transformations were correlated to the analyte structures and properties. Overall, this study presents a new chromatic PDA film system in which noncovalent interactions between the PMMA substrate and spin-coated PDA give rise to distinct chromatic properties and molecular sensing capabilities.

Application of switchable hydrophilicity solvents for recycling multilayer packaging materials

A new procedure based on switchable hydrophilicity solvents (SHS) was proposed for polyethylene and aluminium recovery from food aseptic packaging. Treatment with N,N-dimethylcyclohexylamine (DMCHA) allowed very high material recovery (>99% for aluminium and >80% for polyethylene), without compromising the quality in terms of oxidation or polymer degradation. Moreover, the results from a simplified and preliminary life cycle analysis confirm the potential environmental benefits of a SHS approach compared with other treatment and disposal scenarios.

An efficient route towards a new branched tetrahydrofurane δ-sugar amino acid from a pyrolysis product of cellulose

Abstract(1R,5S)-1-Hydroxy-3,6-dioxa-bicyclo[3.2.1]octan-2-one, is a bicyclic lactone obtained in gram-scale by catalytic pyrolysis of the renewable source cellulose. Now it has been used as a chiral building block in the preparation of the new δ-sugar amino acid, (3R,5S)-5-(aminoethyl)-3-hydroxytetrahydrofurane-3-carboxylic acid, by an efficient synthesis in five steps with a 67% overall yield. The structure of this tetrahydrofurane amino acid, isolated in protonated form, was assigned by extensive mono- and bidimensional 1H- and 13C-NMR analysis and mass spectrometry, including measurements by electrospray and matrix-assisted laser desorption ionization techniques, the latter one for high-resolution experiments. This amino acid is an isoster of dipeptide glycine-alanine (H-Gly-Ala-OH), with a potential use in the access of new peptidomimetics with conformationally restricted structures due to the presence of tetrahydrofurane ring. As a preliminary study in order to disclose this effect, density functional theory calculation performed in water using polar continuum model was applied to the new amino acid and H-Gly-Ala-OH dipeptide, so that to evaluate and compare the relative torsional angles for the energy-minimized structures.

Shaping calcite crystals by means of comb polyelectrolytes having neutral hydrophilic teeth.

Comb polyelectrolytes (CPs) having neutral hydrophilic teeth, similar to double hydrophilic block copolymers, are a powerful tool to modify the chemical-physical properties of inorganic crystalline materials. One of their main applications is in concrete technology, where they work as superplasticizers, particle-dispersing agents. Here, CPs, having the same poly(acrylic acid) (PAA) backbone chain and differing in the grafting with methoxy poly(ethylene glycol) chains (MPEG) of two molecular weights, were used to investigate the influence of tooth chains in polymer aggregation and in control on morphology and aggregation of calcite particles. These polymers aggregate, forming interpolymer hydrogen bonds between carboxylic groups and ether oxygen functionalities. The presence of calcium ions in solution further enhances aggregation. Crystallization experiments of calcite in the presence of CPs show that the specificity of interactions between polymers and crystal planes and control on aggregation and size of particles is a function of the content and chain length of the MPEG in the PAA backbone. These parameters limit and can make specific the electrostatic interactions with ionic crystalline planes. Moreover, the mechanism of crystallization, classical or nonclassical, is addressed by the CP structure and concentration. These findings have implications in the understanding of the complex chemical processes associated to concrete superplasticizers action and in the study of the biomineralization processes, where biological comb polyelectrolytes, the acidic glycoproteins, govern formation of calcitic structures.

Colorimetric analysis of painting materials using polymer-supported polydiacetylene films

Analysis of artworks and identification of their molecular components are of utmost importance for selecting proper conservation strategies and monitoring restoration. Accordingly, development of simple and readily applicable paint analysis assays is highly sought in conservation science and technology. We prepared transparent spin-coated films comprising polydiacetylene (PDA) derivatives upon poly(methyl methacrylate) (PMMA) substrates and employed the PDA/PMMA films for color analysis of organic constituents in painting materials. We show that distinct color transformations were recorded upon addition of paint compounds to different PDA films. Quantitative analysis revealed that the colorimetric transitions were dictated by the interactions between the diacetylene headgroups and the tested compounds. This study underscores the significance of the diacetylene headgroup for molecular discrimination and points to the possible uses of the PMMA-supported PDA films for colorimetric screening of organic components in painting materials.

Ionic liquids effects on the permeability of photosynthetic membranes probed by the electrochromic shift of endogenous carotenoids.

Ionic liquids (ILs) are promising materials exploited as solvents and media in many innovative applications, some already used at the industrial scale. The chemical structure and physicochemical properties of ILs can differ significantly according to the specific applications for which they have been synthesized. As a consequence, their interaction with biological entities and toxicity can vary substantially. To select highly effective and minimally harmful ILs, these properties need to be investigated. Here we use the so called chromatophores--protein-phospholipid membrane vesicles obtained from the photosynthetic bacterium Rhodobacter sphaeroides--to assess the effects of imidazolinium and pyrrolidinium ILs, with chloride or dicyanamide as counter anions, on the ionic permeability of a native biological membrane. The extent and modalities by which these ILs affect the ionic conductivity can be studied in chromatophores by analyzing the electrochromic response of endogenous carotenoids, acting as an intramembrane voltmeter at the molecular level. We show that chromatophores represent an in vitro experimental model suitable to probe permeability changes induced in cell membranes by ILs differing in chemical nature, degree of oxygenation of the cationic moiety and counter anion.