Marco Scoponi

Synthesis and characterization of bisphenol-A copolyethers and copolyesters carrying calix[4]arene units in the main chains and their binding properties towards silver cations

A modified interfacial polycondensation between bisphenol-A and 1,3-dimethoxy lower-rim substituted calix[4]arene derivatives with dibromomethane in the presence of tetrabutylammonium hydrogen sulfate as phase transfer catalyst (PTC) leads to copolyethers with variable M w values depending on the reaction temperature and the amount of PTC. The calix[4]arene content in the polymer chains depends on the phenolic monomer ratios. The polycondensation reaction of the same comonomers with terephthaloyl chloride but in the absence of the above PTC affords the corresponding copolyester. The soluble fraction of this polymeric material in CHCl 3 showed M w of ca. 21000 and a variable calix[4]arene content depending on the phenolic monomer ratio as well. The binding properties of the copolyethers toward silver ions are ten-fold higher than those of a model tetraalkoxy calix[4]arene derivative. It is suggested that this increased receptor ability is due to the change of the original cone conformation of the macrocyclic monomer into the partial-cone conformation by incorporation in the polymer.

Crystal structure and spectroscopic analysis of melamine hydrobromide. Evidence for iso-melamine cations and charge-transfer complexes in the solid state

The crystal structure and vibrational analyses of melamine hydrobromide by FTIR and FT-Raman spectra, are presented. The crystallographic data show π-electron delocalization towards the amino substituents with ring nitrogen protonation in the solid state. Additionally, the presence of intermolecular hydrogen bonding interactions occurring between amino substituents and ring nitrogen lone-pairs gives rise to charge–transfer complexes, as demonstrated by UV–VIS reflectance in the solid state. FTIR and FT-Raman spectra allow the assignments of the vibrational modes in melamine hydrobromide by comparison with the corresponding deuteriated molecules, and show the existence of iso-melamine cations in the solid state.

Degradation of Polyurethane Gastrostomy Devices: What Is the Role of Fungal Colonization?

The aim of this study was to evaluate polyurethane percutaneous endoscopic gastrostomy(PEG) tube degradation and the role played by fungi. The inner surfaces of 20 used polyurethane tubes were brushed, and the brushing end was incubated for 7 days in Saburaud broth and cultured if fungal growth occurred. Three tubes used for 12 (sample 12w), 17 (sample 17w), and 96 (sample 96w) weeks and two new tubes were cut to produce several 4-cm-long equal halves. Six samples from the new tubes were considered control samples (Co sample), seven were incubated in Saburaud broth (Co sample + Sa.), and seven in the broth supplemented with Candida albicans (Co sample + Sa. + Ca). All samples underwent morphological examination by electron microscopy and differential scanning calorimetry measurements (DSC). All tubes had fungal colonization.DSC showed deterioration in all tubes including the new ones; adding Candida albicans had no additional effects. Morphological examination by electron microscopy showed a regular pattern in the Co sample, and thick biofilm, holes, and crevices in samples 12w, 17w, and 96w. The more the tubes had been used, the more severe were the changes. The Co sample + Sa and the Co sample + Sa + Ca showed no changes in the inner surface, but cryogenically fractured surfaces had holes and crevices. Yeasts constantly colonize PEG tubes and are likely to contribute to polyurethane deterioration. The impairment of new PEG tubes incubated in Saburaud broth suggests that other factors also play a role in polyurethane deterioration.

A reappraisal of the photo-oxidation mechanism at short and long wavelengths for poly(2,6-dimethyl-1,4-phenylene oxide)

Abstract A detailed re-examination of the photo-oxidation mechanism of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) at both long and short irradiation wavelengths under accelerated conditions is reported. The formation rate of polydimethylphenoxy (PDMP) radicals is observed both in the presence and in the absence of ultra-violet (u.v.) light by using electron spin resonance spectroscopy. In order to explain the great stability of PDMP radicals, the bimolecular decay observed in the dark is discussed. In addition, spin-trapping experiments using nitrosodurene reveal the existence of benzylic-type radicals under u.v. irradiation conditions. Under mild oxidative conditions, i.e. thermo-oxidation at 80°C, the changes in the Fourier-transform infra-red spectra after 1215 h show the formation of two main absorption bands at 1694 and 1658 cm −1 , assigned to aromatic aldehydes and quinonic groups, respectively. The poor photo-stability of these two primary oxidation products generates, by fast photolytic conversion to benzoic acids and esters. a broad band centred at 1734 cm −1 under accelerated photo-oxidative conditions. Furthermore, the cyclic voltammetry of PPO solution in the dark indicates both the existence of superoxide radical anions in the absence of u.v. light and the electro-catalytic effect possibly induced by quinonic groups. In this work direct formation of radical cations and superoxide anions by a photo-induced electron-transfer reaction is suggested under photo-oxidative conditions. The catalytic role of quinonic groups on the further generation of superoxide anions and PDMP radicals at long irradiation wavelengths and in the dark is also considered on the overall PPO photodegradation.

Photodegradable polyolefins. Photo-oxidation mechanisms of innovative polyolefin copolymers containing double bonds

Abstract Photodegradable polyolefins based on ketone carbonyl and carbon monoxide copolymers are discussed. The proposed photo-oxidation mechanisms for these copolymers show efficient chain scission processes photoinduced by Norrish I and II reaction in polymer matrix. Other polyolefins copolymers containing unsaturation have been suggested as new innovative and photodegradable materials. In the photo-oxidative conditions, the formation of α,β-unsaturated ketone impart high yields of chains scissions leading to a rapid embrittlement and fragmentation of these copolymers.

Plastic debris in the Mediterranean Sea: Types, occurrence and distribution along Adriatic shorelines

Small plastic debris in sediments from five beaches were investigated to evaluate their occurrence and abundance in the Northern Adriatic coast for the first time. Plastic debris extracted from sediments were counted, weighted and identified by Fourier-transform infrared spectroscopy (FT-IR). A total of 1345 items of debris (13.491g) were recorded, with a mean density of 12.1 items kg-1 d.w. and 0.12gkg-1 d.w. Fragments were the most frequent type of small plastics debris detected. In terms of abundance, microplastics (<5mm) accounted for 61% of debris, showing their wide distribution on Adriatic coasts, even far-away from densely populated areas. The majority of the polymers found were polyolefins: there were greater quantities of polyethylene and polypropylene compared to other types of plastic. Primary microplastics accounted for only 5.6% of the total plastic debris. There were greater quantities of microplastics at sites subjected to stronger riverine runoff. The results will provide useful background information for further investigations to understand the sink and sources of this emergent and priority contaminant.

Microplastics in the sediments of Terra Nova Bay (Ross Sea, Antarctica)

This is the first survey to investigate the occurrence and extent of plastic contamination in sediments collected in Terra Nova Bay (Ross Sea, Antarctica). Plastic debris extracted from 31 samples of sediments were counted, weighted and identified by Fourier-transform infrared spectroscopy (FT-IR). All sediment samples contained plastics: a total of 1661 items of debris (3.14g) were recorded from the 31 samples of sediment. Plastic particles in the samples ranged from 0.3 to 22mm in length. Fibres were the most frequent type of small plastics debris detected. In terms of abundance, microplastics (<5mm) accounted for 78.4% of debris. 9 polymer types were found: the most common material (94.13% by weight) was styrene-butadiene-styrene copolymer (SBS), widely used in pneumatic tires, etc. A decreasing concentration of plastic debris at increasing distances from the Mario Zucchelli Base was evidenced.

Photochemical behavior of poly(organophosphazenes). XI. Photochemistry of poly[bis(4-benzylphenoxy) phosphazene]

In this paper we present results on the photolysis of poly[bis(4-benzylphenoxy)-phosphazene] in solution and in film, both in the presence and in the absence of molecular oxygen. Light irradiation of the polymer in oxygen-saturated CH2Cl2 solutions results in a remarkable degradation of the polyphosphazene, while in argon-purged solutions no appreciable variations of the polymer structure could be detected. The photolysis of poly[bis(4-benzylphenoxy)phosphazene] in films induces the cross-linking of the polymer regardless of the presence or the absence of molecular oxygen. The main process observed during the photochemistry both in solution and in the solid state of the polymer is the oxidation of the 4-benzylphenoxy group on the polyphosphazene, without involvement of the inorganic -P=N- backbone. The effect of temperature on the photolysis of the polyphosphazene substrate in film is also reported.

Grafting reactions onto poly(organophosphazenes). II: Photo-induced graft copolymerization of polymethylmethacrylate onto poly[bis(4-isopropylphenoxy)phosphazene]

Abstract This paper presents results on the photo-induced grafting of poly(methyl methacrylate) onto poly[bis(4-isopropylphenoxy)phosphazene], using benzophenone as photoinitiator. The formation of polyphosphazene-g-poly(methyl methacrylate) copolymers was followed by FTIR-ATR spectroscopy, and the products were characterized by contact angle and DSC measurements. Among the parameters affecting the photografting, irradiation time and the ratio methanol/unsaturated monomer used in the grafting experiments are of particular importance.

Grafting reactions onto poly(organophosphazenes)-III. Light-induced graft copolymerization of poly-N,N′-dimethyl-acrylamide onto mobile-hydrogen-containing phosphazene polymers

Abstract In this paper we report the light-induced grafting copolymerization of N , N ′-dimethylacrylamide onto four poly(organophosphazene) films i.e. poly[bis(4-isopropylphenoxy)phosphazene], poly[bis(4-s-butylphenoxy)phosphazene], poly[bis(4-benzylphenoxy)phosphazene] and poly[bis(2,2′,2″-trifluoroethoxy)phosphazene]. The process was carried out in N , N ′-dimethylacrylamide/methanol mixtures in presence of benzophenone as sensitizer. The yield of the grafting process was evaluated as a function of the phosphazene structure, of the relative amounts of N , N ′-dimethylacrylamide and methanol in the reaction mixtures, and of the swelling capability of the polymer films. The obtained polyphosphazene-g-poly- N , N ′-dimethylacrylamide copolymers were characterized by i.r. spectroscopy, both ATR and transmission, and by contact angle measurements.