Allopurinol and its interactions with Cu<Superscript>2+</Superscript> ions: radical reactions and complex structure

Allopurinol (ALP), an inhibitor of the xanthine oxidase enzime, is reported to provide protection against free-radical mediated damage by various mechanisms, including free-radical scavenging and metal chelation (i.e. Cu(II)). To obtain a wider insight into the molecular aspects of the beneficial action of ALP, free ALP and the Cu(II)- ALP system were investigated by radiation chemical and spectroscopic studies. Pulse radiolysis experiments show that ALP is a good · OH scavenger (1.8 × 10⁹ and 5.4 × 10⁹ M^-1 s^-1 at pH 6.0 and 11.0, respectively), leading to · OH-adducts and transient semi-oxidized species, such as phenoxyl radicals. The latter are also formed by the reaction of ALP with some specific one-electron oxidizing radicals (i.e. N₃ and SO₄ ^-). The semi-oxidized species are stabilized by their resonance properties and scarcely react with oxygen. In addition, the chelation of Cu(II) by ALP does not significantly affect the reactivity of the drug towards ·OH (2.5×0⁹ M^-1 s^-1). Raman and the IR spectra support the good chelating ability of ALP, indicating the formation of two Cu(II)- ALP complexes with a slightly different structure. Depending on the metal/ligand ratio, pyrimidine nitrogens may take part to the Cu(II) co-ordination in addition to the N pyrazolic atoms and the C O groups of some ALP molecules. These results suggest that ALP may inhibit oxidative damage both through the direct radical scavenging and the copper-chelation mechanism. In fact, both the conversion of a harmful radical, such as ·OH, into a less reactive transient species, and the capture of copper ions, which play a relevant role in metal-catalysed generation of reactive oxygen species, will prove beneficial for the cell protection.     

One step nanoencapsulation of corrosion inhibitors for gradual release application

The direct application of corrosion inhibitors on metal surfaces is potentially dangerous for the environment and the restoration operators, thus new conservation strategies are mandatory. In this study, two copper corrosion inhibitors, 1H-benzotriazole (BTA) and 5-phenyl-1H-tetrazole (PT), are encapsulated in a silica nanocontainer, for future application in smart coatings, with the aim to reduce the amount of chemicals used in treatments, their dispersion in the environment and the direct exposure of the operators to these chemicals. In particular, composite silica nanocapsules, containing the corrosion inhibitors, are prepared via one-step synthesis, based on mini-emulsion polymerisation processes.The morphology, structure, and texture of these loaded silica nanocontainers are characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N₂ physisorption (BET/BJH). Micro-Raman spectroscopy (RS) is performed to characterise the composition. UV–visible spectroscopy and thermal analysis (TG/DSC) are performed for the loading and encapsulation efficiency (L%, EE%) study.Synthesised nanocapsules show a core-shell structure and, when loaded with the inhibitors, have size ranging from about 130 to 170 nm and a BET surface area of the order of 800 m²/g. The EE% is maximum in the case of BTA and decreases to ～52% in the case of PT.     

Interactions between oligopeptides and oxidised titanium surfaces detected by vibrational spectroscopy

Five alternating polar/hydrophobic oligopeptides derived from EAK 16 (AEAEAKAKAEAEAKAK) were examined in comparison with EAK 16 (peptide 1) both after solubilisation/lyophilisation and deposition on oxidised titanium surfaces. The peptides were synthesised for their possible use as biomimetic materials due to their self‐assembling properties and the presence, in one of them, of the arginine‐glycine‐aspartic (RGD) sequence, an active modulator of cell adhesion. Infrared (IR) and Raman spectroscopies were used to investigate the influence of the amino acid substitution on the self‐assembling properties of the peptides under both experimental conditions. In the lyophilised peptides, β‐sheet was the prevailing conformation (65–69%) as in EAK 16, irrespective of acid substitution (E→D, peptide 2), basic substitution (K→O, peptide 3), hydrophobic spacer substitution (A→Abu, peptide 4 and A→Y, peptide 5) and RGD insertion (peptide 6). After deposition on oxidised titanium, the main conformation remained β‐sheet. The side‐chain shortening of the acidic amino acid residue (peptide 2) or the insertion of a rigid and bulky residue such as Y (peptide 5) decreased the self‐assembling ability more than the side‐chain shortening of the basic amino acid residue (peptide 3) or the insertion of the RGD head (peptide 6). The interaction with the oxidised titanium surface was mainly due to carboxylate groups with a bidentate bridging coordination and C  O peptidic groups. Copyright © 2010 John Wiley & Sons, Ltd.     

Evolution of past enamel technology and metal conservation issues: the case of two Byzantine style bindings

The results of a Raman spectroscopic study of the cloisonne’ and basse‐taille enamels, which beautify two Byzantine style bindings from the Marciana Library (Venice), namely the Lat. III,111 and the MsGR.I.53 codexes, are presented in this work. The first binding dates back to the 13th century and was subject to an early restoration work in the 14th century, when new enamels substituted four originals. The second binding, from the 15th century, shows a lower number of enamels, all originals, and with a larger color palette. The white and yellow enamels of both codexes were successfully characterized and the red ones, where hematite was not used. Interestingly the white and yellow color of the 13th century enamels of the Lat. III,111 codex has been obtained by an ancient technique of the glass technology, which was already obsolete in the 13th century, and is based on the use of calcium antimonate and Naples yellow. The white color in the other binding's enamels have been instead obtained by using cassiterite, according to the tradition of the time. Cassiterite was also mixed to Naples yellow in the enamels of the MsGR.I.53 codex, to change the yellow hue. The identification of agents determining some colors is instead uncertain or not feasible by Raman spectroscopy. The transparency of the 14th century enamels of the Lat. III,111 codex has allowed the comparison of metal degradation below the enamels and in regions exposed to the atmosphere. Copyright © 2012 John Wiley & Sons, Ltd.     

Melatonin: A Neurotrophic Factor?

Melatonin, N-acetyl-5-hydroxytryptamine, is a hormone that synchronizes the internal environment with the photoperiod. It is synthesized in the pineal gland and greatly depends on the endogenous circadian clock located in the suprachiasmatic nucleus and the retina’s exposure to different light intensities. Among its most studied functions are the regulation of the waking-sleep rhythm and body temperature. Furthermore, melatonin has pleiotropic actions, which affect, for instance, the modulation of the immune and the cardiovascular systems, as well as the neuroprotection achieved by scavenging free radicals. Recent research has supported that melatonin contributes to neuronal survival, proliferation, and differentiation, such as dendritogenesis and axogenesis, and its processes are similar to those caused by Nerve Growth Factor, Brain-Derived Neurotrophic Factor, Neurotrophin-3, and Neurotrophin-4/5. Furthermore, this indolamine has apoptotic and anti-inflammatory actions in specific brain regions akin to those exerted by neurotrophic factors. This review presents evidence suggesting melatonin’s role as a neurotrophic factor, describes the signaling pathways involved in these processes, and, lastly, highlights the therapeutic implications involved.     

Influence of concentration and anion size on hydration of H+ ions and water structure

Neutron diffraction experiments with hydrogen isotope substitution on aqueous solutions of HCl and HBr have been performed at concentrations ranging from 1:17 to 1:83 solute per water molecules, at ambient conditions. Data are analyzed using the empirical potential structure refinement technique in order to extract information on both the ion hydration shells and the microscopic structure of the solvent. It is found that the influence of these solutes on the water structure is less concentration dependent than that of salts or hydroxides. Moreover protons readily form a strong H-bond with a water molecule upon solvation, at all proportions. The majority of them is also bonded via a longer bond to another water molecule, giving a prepeak in the g(OwOw). At high solute concentration, the second water molecule may be substituted by the counterion. In particular at solute concentrations of the order of 1:17 or higher, all protons have an anion within a distance of 4.5 A.     

Applications of Raman spectroscopy to library heritage

This work reports some different applications of Raman spectroscopy, a high sensitive non-destructive technique, to the conservation of Library Heritage. By Raman spectroscopy we were able to detect the chemical mechanisms leading to cellulose degradation, identifying the different functional groups formed during the paper ageing. This kind of information is fundamental to choose a suited restoration treatment. A second reported application is the identification of pigments used to decorate paper and parchments. We report some results obtained from analysis of a XV and a XIII century illuminations.     

Non-destructive spectroscopic characterization of parchment documents

Membranaceous substrates - widely found in library heritage - are truly challenging, due to the variety of manufacturing traditions, the intrinsic variability of the animal's skin and the different degradation patterns affecting documents along ageing. Moreover, when dealing with unique and delicate objects as cultural heritage specimens, sampling is never recommended and often explicitly forbidden. Aim of the research presented in this work is to achieve correct protocols for unambiguous characterization of the document's materials chemical structure and of the possible surface treatments.Experimental results allow us to evidence that the chosen non-destructive techniques (Raman, ATR-FTIR and SEM/EDS) provide a good differentiation between parchment manufacturing procedures, western with lime and eastern with enzymatic treatment. Incrustations of salts on the surface as well as superficial treatment with tannin can be clearly detected. Origin of tannin - from the surface or in ink - can also be distinguished.Choice of the better technique is sample-dependent, since preparation methods, degradation, presence of incrustations, amount of tannin, dehairing method can differently affect the spectral features. For instance, Raman appears to be the most effective molecular technique on western parchment, whereas ATR-FTIR allows distinguishing the enzymatic dehairing procedure from the chemical one.