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The derivatisation of materials including iron, gold, and carbon by addition of diazonium salts is a reliable process to tune their interfacial interaction with the surrounding media. In this regard, the functionalisation of carbon nanostructures by diazonium chemistry is a versatile strategy to obtain soluble nanomaterials with degrees of functionalisation among the highest ever reported. Starting from these premises we have studied the functionalisation of multi-walled carbon nanotubes by addition of the aryl diazonium salts generated in situ by treatment of 4-methoxyaniline with isopentylnitrite. Following a thorough purification and characterisation protocol (UV-vis, TGA, ATR-IR, cyclic voltammetry, AFM and other surface analytical techniques), we have investigated the key parameters to obtain both functionalised multi-walled carbon nanotubes, where the amount of functional groups anchored to the carbon surface is less than a monolayer, and superfunctionalised carbon nanotubes, with a carbon nanotube core and a multilayered aryl coating. The results outlined provide the basis for the design and controlled processing of novel decorated carbon nanostructures that would be useful for a number of technological applications. © 2014 Elsevier Ltd. All rights reserved.

In this paper, the synthesis and characterization of novel amphiphilic graft copolymers based on an alpha,beta-poly(N-2-hydroxyethyl)-D, L-aspartamide (PHEA) backbone and D, L-polylactic acid (PLA) hydrophobic side chains are reported. These copolymers were obtained starting from PHEA-ethylenediamine (PHEA-EDA), which was functionalized with polysorbate 80 (PS(80)) and/or PLA in order to obtain the PHEA-EDA-PS(80)-PLA and PHEA-EDA-PLA samples, respectively. The degrees of derivatization, DD(PS80) and DD(PLA), of PHEA-EDA-PS80-PLA, calculated by (1)H-NMR, resulted in being 1.2 +/- 0.03 mol% and 0.54 +/- 0.05 mol%, respectively, while that of PHEA-EDA-PLA was found to be 0.60 +/- 0.05 mol%. Size exclusion chromatography (SEC) analysis confirmed the occurrence of derivatization, the molecular weight values being close to the theoretical ones. Polymeric micelles from PHEA-EDA-PLA and PHEA-EDA-PS(80)-PLA copolymers were obtained by using the dialysis method and were characterized in terms of mean size, zeta potential, critical aggregation concentration (CAC), and surface composition by x-ray photoelectron spectroscopy (XPS) analysis, which demonstrated the presence of PS(80) onto the PHEA-EDA-PS80-PLA micelle surface. In vitro experiments demonstrated that these systems had no cytotoxic effects on 16 HBE, Caco2, HuDe and K562 cell lines, and no haemolytic activity. Moreover, both PHEA-EDA-PS80-PLA and PHEA-EDA-PLA micelles were able to penetrate into Neuro2a cells and, in the case of PS(80) decorated micelles, to escape from phagocytosis by the J774 A1 macrophages.

In this article, the synthesis of two amphiphilic polyaspartamide copolymers, useful to obtain polymeric nanoparticles without using surfactants or stabilizing agents, is described. These copolymers were obtained starting from α,β-poly-(N-2-hydroxyethyl)-dl-aspartamide (PHEA) by following a novel synthetic strategy. In particular, PHEA and its pegylated derivative (PHEA-PEG2000) were functionalized with poly(lactic acid) (PLA) through 1,1′-carbonyldiimidazole (CDI) activation to obtain PHEA–PLA and PHEA-PEG2000–PLA graft copolymers, respectively. These copolymers were properly purified and characterized by 1H-NMR, FT-IR, and Size Exclusion Chromatography (SEC) analyses, which confirmed that derivatization reactions occurred. Nanoparticles were obtained from PHEA–PLA and PHEA-PEG2000–PLA graft copolymers by using the high pressure homogenization-solvent evaporation method, avoiding the use of surfactants or stabilizing agents. Polymeric nanoparticles were characterized by dimensional analysis, before and after freeze-drying process, and Scanning Electron Microscopy (SEM). Zeta potential measurements and X-ray Photoelectron Spectroscopy (XPS) analysis demonstrated the presence of PEG and/or PHEA onto the PHEA-PEG2000–PLA and PHEA–PLA nanoparticle surface, respectively.

In the present work results on the degradation phenomena of stone materials in the Ancient Theatre of Taormina, one of the most important Greek–Roman monuments of Sicily, are reported. Artificial stone materials in different conservation conditions were investigated. Samples of salt efflorescences from brick walls and degraded setting mortars were taken from the open gallery in “summa cavea”. The chemical, physical and structural characterization was performed by means of X-Ray Photoelectron Spectroscopy (XPS), X-Ray Diffraction (XRD) and X-Ray Fluorescence (XRF), both in situ and ex situ. Results showed that the deterioration of stone materials is due to the aggressive action of the environment agents. Soluble salts, such as chlorides, sulphates and nitrates, were found in efflorescence samples. Mortars were affected by a decomposition process induced by sulphates’ attack.

A systematic investigation of the original materials and the degradation phenomena induced by soluble salts on the wall matrix and on the graffiti of the Inquisition jails of Chiaramonte Palace in Palermo (Italy) was carried out. Built in the XIV century, Chiaramonte Palace was used as Inquisition court during the XV–XVI centuries. The ancient graffiti, recently discovered, represent a unique historical witness of the prisoners that lived during that terrible period. In order to study the nature, the amount and the distribution of the salts in the masonry, stone materials sampled at different depth from the wall matrix and saline efflorescences were analysed. Different physical techniques were used, such as X-ray Photoelectron Spectroscopy, X-ray Fluorescence, Laser Induced Breakdown Spectroscopy, X-ray Diffraction and Ionic Chromatography. Results of the chemical and physical characterisation showed that the main cause of the degradation of graffiti and wall paintings was the presence of soluble salts, such as nitrates, chlorides and sulphates. Traces of oxalates, coming from a previous conservation treatment, were also found. The results obtained by the stratigraphical characterisation of soluble salts in the wall matrix can be used to recommend a procedure based on air humidification at high relative humidity values in order to avoid salt crystallisation and to prevent the crumbling process of the graffiti.