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One aspect of heritage science is to examine and, if possible, reduce the chemical and physical interactions between the restoration products and artworks’ constituent materials. This research aims to identify an alternative process to minimize the impact on materials and health risk for users when hypochlorite is used as biocide on stone materials. In this study, we tested a hydrogel comprised of sodium alginate as an inert matrix and hypochlorite ions as biocide agents for the removal of biological patinas from calcarenite Lecce samples. These biofilms resulted formed mainly by filamentous cyanobacteria and green microalgae. We carried out 1H-NMR T2 relaxation measurements to check the hydrogel’s cleaning efficacy on artificially bio-deteriorated samples through a portable NMR equipment. Simultaneously, optical microscopy and colorimetric measurements allowed the establishment of color differences induced by treatments. Our biocide hydrogel proved to be effective in removing microbial colonization from the surface of Lecce stone specimens and from a section of an altar rail in the rupestrian Church of San Pietro Barisano, located in the “Sassi of Matera”.

The effect of differently substituted 2,2'-bipyridine ligands (

The hydrogen bond network has a major role in determining the physical and chemical properties of water both in the solid and in the liquid state. In the bulk liquid phase, there is a coexistence of water molecules with different degrees of coordination and their relative amount changes according to the conditions (

Dipeptides are popular building blocks for supramolecular gels that do not persist in the environment and may find various applications. In this work, we show that a simple substitution on the aromatic side-chain of phenylalanine with either fluorine or iodine enables supramolecular diversity upon self-assembly at neutral pH, leading to hydrogels or crystals. Each building block is characterized by H-1- and C-13-NMR spectroscopy, LC-MS, circular dichroism, and molecular models. The supramolecular behaviour is monitored with a variety of techniques, including circular dichroism, oscillatory rheology, transmission electron microscopy, attenuated total reflectance Fourier-transformed infrared spectroscopy, visible Raman spectroscopy, synchrotron-radiation single-crystal X-ray diffraction and UV Resonance Raman spectroscopy, allowing key differences to be pinpointed amongst the halogenated analogues.

Attenuated total reflection far-ultraviolet (ATR-FUV) spectra in the 145–250 nm region were studied for four kinds of proteins (two α-helix-rich proteins: bovine serum albumin (BSA) and lysozyme and two β-sheet rich proteins: concanavalin A and γ-globulin) in different solutions (pure water and phosphate buffered saline, or PBS) with different concentrations. All the spectra show a band at 191 nm due to the π–π* transition of amide bonds of the proteins. The wavelength of the band does not change with their second structures, suggesting that the corresponding electronic transition mode is localized and polarized in the direction that is not affected by the difference in the peptide folding. The intensity of the 191 nm band differs with the concentration of salt in the solution, suggesting that the band intensity reflects the adsorption density of a protein on the internal reflection element (IRE) made of a sapphire glass prism. According to the intensity changes of the band at 191 nm, it is revealed that the properties in adsorption are different from one protein to another. It is assumed that there are two types of forces on the protein adsorption: one is that among the molecules and the other is that between a molecule and a substrate. The origin of force includes localized electrostatic polarity and affinity to water. The ions in the solvent give a marked effect on these forces, resulting in the difference in the response to adsorption density against the salt concentration in the solvent.

The reaction of CuI(bpy)2 complexes with tBuOOH was followed by a multi-technique approach (DFT-supported lab-scale or synchrotron spectroscopies and electrochemistry). The findings evidence the formation of a CuIIOH species as reactive intermediate.

This study aims at exploring the potential of ATR-far-ultraviolet (FUV) spectroscopy in investigating electronic structure and transitions of various kinds of biological molecules. For this purpose, ATR-FUV spectra were measured for several kinds of proteins with the different secondary structures, several kinds of carbohydrates, nucleic acids, and lipids. Band assignments have been made for all kinds of biological molecules investigated based on our previous ATR-FUV studies on n-alkanes, alcohols, esters, and amides. For example, the proteins show a characteristic band near 200 nm due to π-π* transition of amide groups. The position of this band varies a little with the secondary structure of proteins but its intensity changes significantly depending on the secondary structure and solutions. All the carbohydrates studied yielded a band near 170 nm due to n-Rydberg transition of ether. In addition, acetylcarbohydrates give an additional band near 190 nm originating from π-π* transition of amide at 2’ carbon. The present study has demonstrated that ATR-FUV spectroscopy is a new powerful technique in exploring electronic structure and transitions of biological molecules, in general. It is also possible to use ATR-FUV spectroscopy for quantitative and qualitative analysis of biological molecules. Moreover, it is of note that information regarding electronic transitions collected by ATR-FUV spectroscopy is useful for UV resonance Raman (UVRR) spectroscopy studies of biological molecules. A combined ATR-FUV spectroscopy and UVRR spectroscopy method may provide a novel analytical tool for molecular and electronic structure of biological molecules.

The utility of ionic liquids (ILs) as alternative solvents for stabilizing and preserving the native structure of DNA over the long term may be envisaged for biotechnological and biomedical applications in the near future. The delicate balance between the stabilizing and destabilizing effects of IL-mediated interactions with the structure of DNA is complex and is still not well understood. This work reports a fundamental study dealing with the effect exerted by cations and anions in imidazolium-based ILs on the thermal structural stability of large nucleic acid molecules. Multi-wavelength UV resonance Raman spectroscopy is used for selectively detecting heat-induced structural transitions of DNA localized on specific base tracts. Our study reveals the establishment of preferential interactions between the imidazolium cations of ILs and the guanine bases in the DNA groove that lead to more effective stacking between the guanine bases even at high temperatures. Interestingly, we observe that this trend for ILs sharing the same chloride anion is further enhanced as the alkyl chain on the imidazolium cation gets shorter. The results from the present investigation lead to a more comprehensive view of the IL-mediated interactions with A-T and G-C base pairs during thermal unfolding.

The hydrogen bonding of water and water/salt mixtures around the proline-based tripeptide model glycyl-l-prolyl-glycinamide·HCl (GPG-NH2) is investigated here by multi-wavelength UV resonance Raman spectroscopy (UVRR) to clarify the role of ion–peptide interactions in affecting the conformational stability of this peptide. The unique sensitivity and selectivity of the UVRR technique allow us to efficiently probe the hydrogen bond interaction between water molecules and proline residues in different solvation conditions, along with its influence on trans to cis isomerism in the hydrated tripeptide. The spectroscopic data suggest a relevant role played by the cations in altering the solvation shell at the carbonyl site of proline., while the fluoride and chloride anions were found to promote the establishment of the strongest interactions on the C=O site of proline. This latter effect is reflected in the greater stabilization of the trans conformers of the tripeptide in the presence of these specific ions. The molecular view provided by UVRR experiments was complemented by the results of circular dichroism (CD) measurements that show a strong structural stabilizing effect on the β-turn motif of GPG-NH2 observed in the presence of KF as a co-solute.

Glues based on starch are widely used for the consolidation of brittle fibres in historic and archaeological textiles. Ageing fabrics are affected by hydrolysis/oxidation and cross-linking of these glues, a decrease of glues' solubility, the formation of cracks, and discoloration. The hydrolytic action of enzymes on starch-based glues is promising, as molecular recognition offers great selectivity. However, a systematic assessment of the best methods for applying enzymatic formulations has not been explored yet. Here, α-amylase was applied either by pipetting a solution or combining with gellan gel (embedded in the gel or spread on the gel surface). The effectiveness of the different formulations on the removal of potato and wheat starch was evaluated by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and colorimetric measurements. Enzymes dispersed in gel showed weak diffusion at the surface, resulting in poor starch breakdown and removal. On the contrary, amylase applied by pipette and spread on gel resulted in high starch removal selectivity and efficiency, with neither swelling nor damage to the fibres. These results validate protocols for the assessment of the enzymatic activity on glue-consolidated fibres, identify best application methods and confirm the excellent properties of amylase dispersions for the conservation of historic and archaeological textiles.Key points• Application of α-amylase by pipette and combined with gellan gel to remove starch glues from wool.• Systematic assessment of the best application methods following a multi-analytical protocol.• Enzymes dispersed in gel exhibit poor diffusion at the surface, leading to weak starch removal.• Enzymes applied by pipette and spread on gel are efficient in starch cleaning, without damage to the fibres.

The object of the work is a character of the Madonna con Bambino (XIII–XV century) mural painting (Fontecchio – L’Aquila, Italy). It was analyzed by different nondestructive testing (NDT) techniques: electronic speckle pattern interferometry (ESPI), ultraviolet (UV) imaging and infrared vision. In addition, three micro-samplings were collected on suspected areas after examination of the signal strength variations over the raw thermograms. On the latter, the images’ quality was enhanced by applying advanced processing techniques. Micro-samplings were also analyzed by scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared (FTIR) and μ-Raman spectroscopy. Splitting, subsurface cracks and under-/over-paintings were detected by this integrated method.

The aim of this work is to evaluate the potentiality of a multi-technique nondestructive approach for characterizing the state of conservation of precious bookbindings. In particular, the bookbinding of an ancient book dating back nineteenth century was inspected by infrared thermography, near-infrared reflectography and transmittography, digital speckle photography, holographic interferometry, and proton magnetic resonance relaxometry. Data were processed by different and innovative methodologies, among which, a calibration procedure of the camera for correlation analyses based on specklegrams. The results were compared, showing a promising synergy for the diagnostic purposes, on the basis of the relationship between structure, properties, and uses of the analyzed materials.

The present work is focused on the γ-radiation induced polymerization of ethyl methacrylate (EMA) and methyl acrylate (MA) monomers mixture to obtain a co-polymer with specific features. The effect of the irradiation parameters (radiation absorbed dose, dose rate) and of the environmental atmosphere on the features of the final products was investigated. Attenuated Total Reflectance - Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Nuclear Magnetic Resonance high-resolution analyses of hydrogen and carbon nuclei (1H and 13C NMR) were applied to follow the γ-induced modifications by monitoring the co-polymerization process and allowed the irradiation parameters optimization. Diffusion-Ordered NMR (DOSY-NMR) data were used to evaluate the co-polymers polydispersity and polymerization degree. Since the last parameter is strongly influenced by the γ radiation and environmental conditions, a comparison among samples prepared and irradiated in air and under nitrogen atmosphere was carried out. In presence of oxygen, higher radiation was required to obtain a full solid co-polymer since a partial amount of energy released to the samples was involved in competitive processes, i.e. oxygen-containing free radicals formation and primary radicals recombination. Irrespectively to the environmental atmosphere, more homogeneous samples in term of polymerization degree dispersion was achieved at lower dose rates. At radiation absorbed doses higher than those needed for the formation of the co-polymer, while in case of samples irradiated in air heavy depolymerization was verified, a sensible increase of the samples stability was attained if the irradiation was performed under nitrogen atmosphere. © 2017 Elsevier Ltd

In this paper, chemical and structural studies of medieval wall paintings in Ocre (L’Aquila, Italy) are presented. During the latest restoration campaign, non-destructive (Near-Infrared Reflectography and Infrared Thermography) and micro-invasive (Nuclear Magnetic Resonance, Fourier Transform Infrared Spectroscopy, μ-Raman, Scanning Electron Microscopy with X-ray Microanalysis, X-Ray Diffraction, X-Ray Fluorescence, Optical Microscopy, Mass Spectrometry, Thermogravimetry) analyses were performed in order to determine the detachments of wall surfaces and the characterization of original and restoration materials. Data integration allowed to reconstruct the conservative history, the execution techniques and the conservation problems of the artefact, as well as to assess the effectiveness of restoration activities adopted. The combined use of physical and micro-chemical techniques proved to be effective for an in-depth study of materials stratification of paintings.