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Polydopamine has the capacity to adhere to a large variety of materials and this property offers the possibility to bind nanoparticles to solid surfaces. In this work, magnetite nanoparticles were deposited on gold substrates coated with polydopamine films. The aim of this work was to investigate the effects of the composition and morphology of the PDA layers on the sticking of magnetite nanoparticles. The polydopamine coating of gold surfaces was achieved by the oxidation of alkaline solutions of dopamine with various reaction times. The length of the reaction time to form PDA was expected to influence the composition and surface roughness of the PDA films. Magnetite nanoparticles were deposited on these polydopamine films by immersing the samples in aqueous dispersions of nanoparticles. The morphology at the nanometric scale and the composition of the surfaces before and after the deposition of magnetite nanoparticles were investigated by means of AFM and XPS. We found that the amount of magnetite nanoparticles on the surface did not vary monotonically with the reaction time of PDA formation, but it was at the minimum after 20 min of reaction. This behavior may be attributed to changes in the chemical composition of the coating layer with reaction time.

Abstract Alkaptonuria (AKU), a rare genetic disorder, is characterized by the accumulation of homogentisic acid (HGA) in organs due to a deficiency in functional levels of the enzyme homogentisate 1,2-dioxygenase (HGD), required for the breakdown of HGA, because of mutations in the HGD gene. Over time, HGA accumulation causes the formation of the ochronotic pigment, a dark deposit that leads to tissue degeneration and organ malfunction. Such behaviour can be observed also in vitro for HGA solutions or HGA-containing biofluids (e.g. urine from AKU patients) upon alkalinisation, although a comparison at the molecular level between the laboratory and the physiological conditions is lacking. Indeed, independently from the conditions, such process is usually explained with the formation of 1,4-benzoquinone acetic acid (BQA) as the product of HGA chemical oxidation, mostly based on structural similarity between HGA and hydroquinone that is known to be oxidized to the corresponding para-benzoquinone. To test such correlation, a comprehensive, comparative investigation on HGA and BQA chemical behaviours was carried out by a combined approach of spectroscopic techniques (UV spectrometry, Nuclear Magnetic Resonance, Electron Paramagnetic Resonance, Dynamic Light Scattering) under acid/base titration both in solution and in biofluids. New insights on the process leading from HGA to ochronotic pigment have been obtained, spotting out the central role of radical species as intermediates not reported so far. Such evidence opens the way for molecular investigation of HGA fate in cells and tissue aiming to find new targets for Alkaptonuria therapy.

The size, size distribution and magnetic properties of magnetite nanoparticles (NPs) prepared by co-precipitation without citrate, in the presence of citrate and citrate adsorbed post-synthesis were studied by X-ray Diffraction (XRD), Dynamic Light Scattering (DLS), Electron Paramagnetic Resonance (EPR) and magnetization measurements. The aim of this investigation was to clarify the effect of citrate ions on the size and magnetic properties of magnetite NPs. The size of the primary NPs, as determined by analysing the width of diffraction peaks using various methods, was ca. 10 nm for bare magnetite NPs and with citrate adsorbed post-synthesis, whereas it was around 5 nm for the NPs co-precipitated in the presence of citrate. DLS measurements show that the three types of NPs form aggregates (100–200 nm in diameter) but the dispersions of the citrate-coated NPs are more stable against sedimentation than those of bare NPs. The sizes and size distributions determined by XRD are in good agreement with those of the magnetic domains obtained by fitting of the magnetization vs. magnetic field intensity curves. Magnetization vs. magnetic field intensity curves show that the three kinds of sample are superparamagnetic.

The chemical characterization of gilding decorations in works of art is fundamental in order to elucidate the techniques and materials used by the artists. In the present work we investigated by a combination of bulk and surface sensitive methods the composition and micro stratigraphy of the gilding laminae in the wall painting of the 14th century “La Maestà”, the masterpiece of Simone Martini. The aim of this study was to determine the composition of the gilding leaves and of the adhesive organic materials used to glue the metallic decorations to the wall painting. Due to the altered state of the samples we could not univocally identify the nature of the adhesive materials. Time of flight secondary ion mass spectrometry measurements showed that the gilding layers consisted of a gold leaf which was laid either directly on a preparation layer or on a tin lamina. The high sensitivity of ToF-SIMS and its spatial resolution allowed us to find traces of silver in the gold leaves and in the tin laminae which were not revealed by energy dispersive X-ray analysis.

Poly(N-isopropylacrylamide) (PNIPAM) hydrogels containing carboxymethylcellulose (CMC) and CMC/Fe3O4 nanoparticles were prepared. Free-radical polymerization with BIS as cross-linker was used to synthesize the hydrogels. The morphology at the microscopic scale of these materials was investigated using field emission scanning electron microscopy (FESEM). The images show that CMC in the PNIPAM hydrogels induces the formation of a honeycomb structure. This surface morphology was not observed for pure PNIPAM hydrogels prepared under similar conditions. The equilibrium swelling degree of the PNIPAM/CMC hydrogels (5200%) is much larger than that of the pure PNIPAM hydrogels (2500%). The water retention of PNIPAM/CMC hydrogels above the volume phase transition temperature is strongly reduced compared to that of pure PNIPAM hydrogel. Both PNIPAM/Fe3O4 and PNIPAM/CMC/Fe3O4 hydrogels exhibit a superparamagnetic behavior, but the blocking temperature (104 K) of the former is higher than that of the latter (83 K).

The aim of this study was to find a novel simple method to obtain polysaccharide ultrathin layers on solid substrates to investigate the interaction between the surface and the biological environment. A Hyaluronan (Hyal) monolayer with a well-defined chemistry was obtained by exploiting the capability of organosilanes to spontaneously adhere onto glass surfaces. A silane alkylic chain was conjugated with Hyal, and the derivatized polysaccharide was allowed to spontaneously adhere onto a glass surface. The elemental analysis of the modified polysaccharide demonstrated that one out of five disaccharide units was conjugated with the alkyl silane chain, corresponding to a substitution degree of the carboxylate groups of ∼20%. The film of the modified polysaccharide was characterized by means of X-ray photoelectron spectroscopy (XPS), water contact angle, and atomic force microscopy (AFM) measurements. XPS analysis demonstrated that we obtained a Hyal layer with a thickness of about 2.0 nm corresponding to a Hyal monolayer. The Hyal-coated surfaces appeared to be rather smooth and highly hydrophilic and showed significant resistance to nonspecific cell adhesion. [ABSTRACT FROM AUTHOR]