Polymer Blends Based on 1-Hexadecyl-3-methyl Imidazolium 1,3-Dimethyl 5-Sulfoisophthalate Ionic Liquid: Thermo-Mechanical, Surface Morphology and Antibacterial Properties.

In this study, antibacterial polymer blends based on Polyvinyl Chloride (PVC) and Polystyrene-Ethylene-Butylene-Styrene (SEBS), loaded with the ionic liquid (IL) 1-hexadecyl-3-methyl imidazolium 1,3-dimethyl 5-sulfoisophthalate (HdmimDMSIP) at three different concentrations (1%, 5%, and 10%), were produced. The IL/blends were characterized by their thermo-mechanical properties, surface morphology, and wettability. IL release from the blends was also evaluated. The agar diffusion method was used to test the antibacterial activity of the blends against Staphylococcus epidermidis and Escherichia coli. Results from thermal analyses showed compatibility between the IL and the PVC matrix, while phase separation in the SEBS/IL blends was observed. These results were confirmed using PY-GC MS data. SEM analyses highlighted abundant IL deposition on PVC blend film surfaces containing the IL at 5-10% concentrations, whereas the SEBS blend film surfaces showed irregular structures similar to islands of different sizes. Data on water contact angle proved that the loading of the IL into both polymer matrices induced higher wettability of the blends' surfaces, mostly in the SEBS films. The mechanical analyses evidenced a lowering of Young's Modulus, Tensile Stress, and Strain at Break in the SEBS blends, according to IL concentration. The PVC/IL blends showed a similar trend, but with an increase in the Strain at Break as IL concentration in the blends increased. Both PVC/IL and SEBS/IL blends displayed the best performance against Staphylococcus epidermidis, being active at low concentration (1%), whereas the antimicrobial activity against Escherichia coli was lower than that of S. epidermidis. Release data highlighted an IL dose-dependent release. These results are promising for a versatile use of these antimicrobial polymers in a variety of fields.

Full Recycling and Re-Use of Bio-Based Epoxy Thermosets: Chemical and Thermomechanical Characterization of the Recycled Matrices.

High performances of thermosets deriving from their covalent intermolecular cross-link bonds result in their low recyclability hindering the full exploitation of a truly circular approach for cured thermosets. In this experimental work, the recyclability of a bio-based fully recyclable epoxy resin using a mild chemical recycling process was demonstrated. The recycled polymer obtained was fully characterized to ascertain its structure and properties. MALDI (Matrix-Assisted Laser Desorption/Ionization), GPC (Gel Permeation Chromatography) and NMR (Nuclear Magnetic Resonance) spectroscopy to determine the chemical structure of the recycled polymer were used. The thermomechanical properties of the cured virgin network and of the recycled product obtained were measured by DSC (Differential Scanning Calorimetry) and DMA (Dynamic Mechanical Analysis). Thermogravimetric analysis of the recycled polymer was also performed. The recycled polymer was transformed into a polyurethane by reacting it with an isocyanate. The synthetized polyurethane obtained therefrom was thoroughly characterized by thermogravimetric analysis. This approach proved the possibility to up-scale the recycled product making it available for novel applications exploiting its re-use.

Thermo-mechanical, antimicrobial and biocompatible properties of PVC blends based on imidazolium ionic liquids.

The aim of this study was the development of antimicrobial polyvinylchloride (PVC) blends loaded with 0.1-10% (w/w) of the ILs 1-hexadecyl-3-methylimidazolium 1,3-dimethyl 5-sulfoisophthalate (HdmimDMSIP) and 1-octyloximethyl-3-methylimidazolium hexafluorophosphate (OOMmimPF6). The synthetized ILs were characterized by 1HNMR, MALDI-TOF, DSC and TGA. PVC/ILs films were obtained by solvent casting.Thermal and mechanical properties (tensile stress TS and elongation at break EB), morphology by SEM, surface wettability, antimicrobial activity, cytotoxicity and ILs release in sterile water from PVC/ILs film blends were determined. Results demonstrated that the presence of both ILs in PVC formulation slightly affected thermal and mechanical properties of blends. The loading of both ILs into PVC matrix made PVC/ILs films hydrophilic, especially at the highest concentration of HdmimDMSIP. The PVC/ILs blends displayed antibacterial activity up to ILs lowest concentrations (0.1-0.5%). The inhibition of Escherichia coli growth was lower than that showed toward Staphylococcus epidermidis. The addition of 10% ILs concentration resulted excessive as demonstrated by accumulation of ILs on film surfaces (SEM) and ILs high release from PVC/ILs blends during the first day of water immersion. Biocompatibility studies highlighted that the addition of low amounts of both ILs into PVC matrix is not cytotoxic for mouse fibroblast cells (L929), supporting their potential use for biomedical porposes.

Thermal Degradation Processes of Aromatic Poly(Ether Sulfone) Random Copolymers Bearing Pendant Carboxyl Groups.

Thermal degradation processes of poly(ether sulfone) random copolymers having different molar amount of diphenolic acid (DPA) units were studied by direct-pyrolysis/mass spectrometry, stepwise pyrolysis-gas chromatography/mass spectrometry and thermogravimetric techniques. Results highlighted that thermal degradation processes occur in the temperature range from 370 to 650 °C, yielding a char residue of 32-35 wt%, which decreases as the mol% of DPA units rises. The pyrolysis/mass spectra data allowed us to identify the thermal decomposition products and to deduce the possible thermal degradation mechanisms. Thermal degradation data suggest that the decarboxylation process of the pendant acid moiety mainly occurs in the initial step of the pyrolysis of the copolymers studied. Successively, the scission of the generated isobutyl groups occurs in the temperature range between 420 and 480 °C. Known processes involving the main chain random scission of the diphenyl sulfone and diphenyl ether groups were also observed.

Synthesis and Characterization of Copoly(Ether Sulfone)s with Different Percentages of Diphenolic Acid Units.

New functionalized Poly(ether sulfone)s having different molar ratio (10, 20, 30, 50, 70, 100 mol%) of 4,4-bis phenoxy pentanoic acid unit (diphenolic acid; DPA) units were synthesized and characterized by (1H and 13C)-NMR, MALDI-TOF MS, FT-IR, DSC and DMA analyses. The microstructural analysis of the copolymers, obtained by 13C-NMR using an appropriate statistical model, shows a random distribution of copolymer sequences, as expected. The presence of different amount of DPA units along the polymer chains affects the chemical and physical properties of the copolymers. The Tg and the contact angle values decrease as the molar fraction of DPA units increases, whereas the hydrophilicity increases. NMR and MALDI-TOF MS analyses show that all polymer chains are almost terminated with hydroxyl and chlorine as end groups. The presence of cyclic oligomers was also observed by MALDI-TOF MS analysis.

Orientation behavior is a good biomarker of trace metal contamination in Parallelomorphus laevigatus (Coleoptera, Carabidae).

Behavioral ecotoxicology has become very important in the short time since a change in behavior is very often the first response to environmental altered conditions. We investigated the influence of trace metal intake on the spatial orientation performances of the carabid beetle Parallelomorphus laevigatus, fundamental ability for its survival. The aim of this study was to consider the solar orientation as behavioral biomarker for exposure to trace metal contamination. Therefore, we tested the ability of solar orientation of specimens of this species, fed with shrimps contaminated with three different concentrations of Cu, Zn, or Hg. We carried out the orientation tests after 1, 3, 7, and 10 days of contaminated feeding. Subsequently, we fed these beetles with not contaminated shrimps and again tested them after 1, 3, 7, and 10 days. For all three metals considered and, regardless of the degree of contamination of the food, we have found a progressive and significant counterclockwise displacement of the angle of orientation and a corresponding progressive reduction in the precision in the directional choices by the animals. We also noticed a clear growing recovery in the normal orientation by these insects after returning to their feeding with uncontaminated food. In conclusion, we can consider the orientation in space of P. laevigatus as a behavioral biomarker for exposure to trace metal contamination. We believe that the intake of trace metals may induce the insects to make mistakes in their spatial orientation, due to an acceleration of their biological clock. Such a clock malfunction is not definitive, since the return to a normal diet restores P. laevigatus the ability to re-make the correct directional choices. Ultimately, our results confirm the usefulness of behavioral ecotoxicology investigations; moreover, they stimulate the opportunity to deepen the understanding of functioning of the biological clock in the animals.

The ground beetle Parallelomorphus laevigatus is a potential indicator of trace metal contamination on the eastern coast of Sicily.

Carabids are generally considered to be non-specialized predators, and they have been considered useful ecological indicators. They can play a key role in clarifying the route of contaminants in food webs because they are predators of small invertebrates and, in turn, part of the diet of several vertebrates. The Mediterranean species Parallelomorphus laevigatus, which so far has not been studied from an ecotoxicological point of view, is an excellent ecological indicator in sandy coastal environments. We investigated the accumulation of trace elements in Ionian populations of P. laevigatus and evaluated the transfer of metal through the food chain of the coastal ecosystem. We analyzed 15 metals, including 11 essential metals (Co, Cr, Cu, Fe, Mn, Mo, Ni, Se, Sn, V and Zn) and four toxic metals (As, Cd, Hg and Pb). Significant differences were found in metal concentration in animal tissues among sites. Our results support the existence of defense mechanisms for the studied species. High values of As, Cd, Cr, Pb, Ni, and Hg detected in the beetles from the control site can be explained by both the emission sources from the nearby industrial plants and the intense agricultural activity. The present paper shows increasing Hg concentrations in the simplified trophic web of sandy beaches and confirms the capability of this pollutant to biomagnify. Moreover, the high value of biomagnification factor (BMF) points to the severe pollution level in this protected area.

Bioaccumulation of trace elements in the sandhopper Talitrus saltator (Montagu) from the Ionian sandy coasts of Sicily.

The Ionian beaches of Sicily are of particular ecological interest because they include the basin of the largest active volcano in Europe and hosts both sites subject to natural protection constraints, as well as important industrial settlements. Consequently, the possibilities for these areas to become polluted are numerous. The sandhopper Talitrus saltator has proven to be a good bioindicator of contamination by numerous trace metals on some European coasts. Nevertheless, no data are available for the populations inhabiting the shores of the southern Mediterranean. Now, as metal accumulation has been shown to vary intraspecifically, the aim of this study was to evaluate trace metal accumulation in adults of T. saltator inhabiting Ionian coastal areas of Sicily and make an assessment of natural and anthropogenic metal pollution of this strip of coast. We also extended our survey to As, Co, Mo, Se, Sn and V never investigated before in this species. Significant differences in metal concentration among sites were found in both sand samples and amphipod tissues. The highest metal content was observed near the mouth of Simeto, the longest river of Sicily which collects waters coming from the volcanic territory of Mount Etna. The bioaccumulation of Cd, Cu, Hg and Zn in T. saltator is fully confirmed; it is also proven for As and Mo and assumed for Cr, Fe, Mn and V. Our outcomes let us to evaluate the prevailing influence of telluric contamination of the Ionian sandy shores of Sicily by trace metals. We also come to the conclusion that in the northern sites, pollution originates from volcanic emission while anthropogenic influence prevails in the southern ones.

Structural characterization of synthetic poly(ester amide) from sebacic acid and 4-amino-1-butanol by matrix-assisted laser desorption ionization time-of-flight/time-of-flight tandem mass spectrometry.

Matrix-assisted laser desorption/ionization time-of-flight/time-of-flight tandem mass spectrometry (MALDI-TOF/TOF-MS/MS) was employed to analyze a poly(ester amide) sample (PEA-Bu) from the melt condensation of sebacic acid and 4-amino-1-butanol. In particular, we investigated the fragmentation pathways, the ester/amide bond sequences and the structure of species derived from side reactions during the synthesis. MALDI-TOF/TOF-MS/MS analysis was performed on cyclic species and linear oligomers terminated by dicarboxyl groups, carboxyl and hydroxyl groups and diamino alcohol groups. The sodium adducts of these oligomers were selected as precursor ions. Different end groups do not influence the fragmentation of sodiated poly(ester amide) oligomers and similar series of product ions were observed in the MALDI-TOF/TOF-MS/MS spectra. According to the structures of the most abundant product ions identified, the main cleavages proceed through a beta-hydrogen-transfer rearrangement, leading to the selective scission of the --O--CH2-- bonds. Abundant product ions originating from --CH2--CH2-- (beta-gamma) bond cleavage in the sebacate moiety were also detected. Their formation should be promoted by the presence of an alpha,beta-unsaturated ester or amide end group. MALDI-TOF/TOF-MS/MS provided structural information concerning the ester/amide sequences in the polymer chains. In the MALDI-TOF/TOF-MS/MS spectra acquired, using argon as the collision gas, of cyclic species and linear oligomers terminated by diamino alcohol groups, product ions in the low-mass range, undetected in the mass spectra acquired using air as the collision gas, proved to be diagnostic and made it possible to establish the presence of random sequences of ester and amide bonds in the poly(ester amide) sample. Furthermore, MALDI-TOF/TOF-MS/MS provided useful information to clarify the structures of precursor ions derived from side reactions during the synthesis.

Matrix-assisted laser desorption/ionization time-of-flight/time-of-flight tandem mass spectra of poly(butylene adipate).

Matrix-assisted laser desorption/ionization time-of-flight/time-of-flight tandem mass spectrometry (MALDI-TOF/TOF-MS/MS) was employed to analyze four poly(butylene adipate) (PBAd) oligomers and to investigate their fragmentation pathways as a continuation of our work on the MALDI-TOF/TOF-MS/MS study of synthetic polymers. MALDI-TOF/TOF-MS/MS analysis was performed on oligomers terminated by carboxyl and hydroxyl groups, methyl adipate and hydroxyl groups, dihydroxyl groups, and dicarboxyl groups. The sodium adducts of these oligomers were selected as precursor ions. Different end groups do not influence the fragmentation of sodiated polyester oligomers and similar series of product ions were observed in all the MALDI-TOF/TOF-MS/MS spectra. According to the structures of the most abundant product ions identified in the present work, three fragmentation pathways have been proposed to occur most frequently in PBAd: beta-hydrogen-transfer rearrangement, leading to the selective cleavage of the --O--CH(2)-- bonds; --CH(2)--CH(2)-- (beta--beta) bond cleavage in the adipate moiety; and ester bond scission.

Sequence determination in aliphatic poly(ester amide)s by matrix-assisted laser desorption/ionization time-of-flight and time-of-flight/time-of-flight tandem mass spectrometry.

Poly(ester amide)s from dimethyl sebacate or sebacic acid and 2-aminoethanol or 4-amino-1-butanol were characterized by post-source decay matrix-assisted laser desorption/ionization time-of-flight (PSD-MALDI-TOF) and time-of-flight/time-of-flight tandem mass spectrometry (MALDI-TOF/TOF-MS/MS). Sodiated oligomers were selected as precursor ions for dissociation studies. PSD analysis was performed on dimethyl sebacate, dicarboxylic, carboxylic and amino alcohol, and diamino alcohol terminated oligomers. PSD-MALDI-TOF mass spectra yielded information on the fragmentation mechanisms of the poly(ester amide) chains, showing that the main cleavages proceed through a beta-hydrogen transfer rearrangement. MALDI-TOF/TOF-MS/MS provided structural information concerning ester/amide sequences in the polymer chains. As expected, together with the ions appearing in the PSD-MALDI mass spectrum, several new abundant fragment ions in the low-mass range are present in MALDI-TOF/TOF-MS/MS spectra. These new product ions proved to be diagnostic and made it possible to establish the presence of random sequences of ester and amide bonds in the poly(ester amide)s samples.