Bacterial Nanocellulose Hydrogel for the Green Cleaning of Copper Stains from Marble.

Cultural heritage stone materials frequently experience significant discoloration induced by copper corrosion products, especially calcareous stones associated with bronze or copper statues and architectural elements. This alteration originates from the corrosion of unprotected copper, resulting in the formation of various Cu minerals and the migration of soluble ions to adjacent stone materials. Traditional cleaning methods involve mechanical, chemical, and laser techniques, which are generally time-consuming, costly, not ecological, or can possibly damage original materials. The loading of highly effective chelating agents, such as ethylenediaminetetraacetic acid (EDTA), into hydrogels has recently been exploited. However, the preference for synthetic hydrogels has been prominent until now, although they lack renewability and biodegradability and require high costs. This study explores for the first time the potential to clean copper corrosion with bacterial nanocellulose (BC) loaded with EDTA as a biologically based, sustainable, and biodegradable hydrogel. The BC hydrogel was characterised by field emission-scanning electron microscopy (FE-SEM), X-ray diffraction analysis (XRD), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), simultaneous thermal analysis (TG-DSC), and tensile testing. It revealed a nano-fibrous structure with high crystallinity and purity and mechanical properties suitable for cultural heritage applications. The EDTA-loaded hydrogel effectively removed copper stains from marble after 120 min of application. Micro-Raman and colorimetric analyses assessed the cleaning efficacy. The study introduces bacterial nanocellulose as a green and effective alternative for heritage conservation, aligning with sustainable methodologies in stone conservation.

Considerations on chemical composition of psammoma bodies: Automated detection strategy by infrared microspectroscopy in ovarian and thyroid cancer tissues.

Ectopic calcifications are observed in many soft tissues and are associated with several diseases, including cancer. The mechanism of their formation and the correlation with disease progression are often unclear. Detailed knowledge of the chemical composition of these inorganic formations can be very helpful in better understanding their relationship with unhealthy tissue. In addition, information on microcalcifications can be very useful for early diagnosis and provide insight into prognosis. In this work the chemical composition of psammoma bodies (PBs) found in tissues of human ovarian serous tumors was examined. The analysis using Micro Fourier Transform Infrared Spectroscopy (micro-FTIR) revealed that these microcalcifications contain amorphous calcium carbonate phosphate. Moreover, some PB grains showed the presence of phospholipids. This interesting result corroborates the proposed formation mechanism reported in many studies according to which ovarian cancer cells switch to a calcifying phenotype by inducing the deposition of calcifications. In addition, other techniques as X-ray Fluorescence Spectroscopy (XRF), Inductively Coupled Plasma Optical Emission Spectroscopy(ICP-OES) and Scanning electron microscopy (SEM) with Energy Dispersive X-ray Spectroscopy (EDX) were performed on the PBs from ovary tissues to determine the elements present. The PBs found in ovarian serous cancer showed a composition comparable to PBs isolated from papillary thyroid. Based on the chemical similarity of IR spectra, using micro-FTIR spectroscopy combined with multivariate analysis, an automatic recognition method was constructed. With this prediction model it was possible to identify PBs microcalcifications in tissues of both ovarian cancers, regardless of tumor grade, and thyroid cancer with high sensitivity. Such approach could become a valuable tool for routine macrocalcification detection because it eliminates sample staining, and the subjectivity of conventional histopathological analysis.

Functionalization of Commercial Electrospun Veils with Zinc Oxide Nanostructures.

The present research is focused on the synthesis of hexagonal ZnO wurtzite nanorods for the decoration of commercially available electrospun nylon nanofibers. The growth of ZnO was performed by a hydrothermal technique and for the first time on commercial electrospun veils. The growth step was optimized by adopting a procedure with the refresh of growing solution each hour of treatment (Method 1) and with the maintenance of a specific growth solution volume for the entire duration of the treatment (Method 2). The overall treatment time and volume of solution were also optimized by analyzing the morphology of ZnO nanostructures, the coverage degree, the thermal and mechanical stability of the obtained decorated electrospun nanofibers. In the optimal synthesis conditions (Method 2), hexagonal ZnO nanorods with a diameter and length of 53.5 nm ± 5.7 nm and 375.4 nm ± 37.8 nm, respectively, were obtained with a homogeneous and complete coverage of the veils. This easily scalable procedure did not damage the veils that could be potentially used as toughening elements in composites to prevent delamination onset and propagation. The presence of photoreactive species makes these materials ideal also as environmentally friendly photocatalysts for wastewater treatment. In this regard, photocatalytic tests were performed using methylene blue (MB) as model compound. Under UV light irradiation, the degradation of MB followed a first kinetic order data fitting and after 3 h of treatment a MB degradation of 91.0% ± 5.1% was achieved. The reusability of decorated veils was evaluated and a decrease in photocatalysis efficiency was detected after the third cycle of use.

Antibacterial Effect of Zinc Oxide-Based Nanomaterials on Environmental Biodeteriogens Affecting Historical Buildings.

The colonization of microorganisms and their subsequent interaction with stone substrates under different environmental conditions encourage deterioration of materials by multiple mechanisms resulting in changes in the original color, appearance and durability. One of the emerging alternatives to remedy biodeterioration is nanotechnology, thanks to nanoparticle properties such as small size, no-toxicity, high photo-reactivity, and low impact on the environment. This study highlighted the effects of ZnO-based nanomaterials of two bacteria genera isolated from the Temple of Concordia (Agrigento's Valley of the Temples in Sicily, Italy) that are involved in biodeterioration processes. The antimicrobial activities of ZnO-nanorods (Zn-NRs) and graphene nanoplatelets decorated with Zn-NRs (ZNGs) were evaluated against the Gram positive Arthrobacter aurescens and two isolates of the Gram negative Achromobacter spanius. ZNGs demonstrated high antibacterial and antibiofilm activities on several substrates such as stones with different porosity. In the case of ZNGs, a marked time- and dose-dependent bactericidal effect was highlighted against all bacterial species. Therefore, these nanomaterials represent a promising tool for developing biocompatible materials that can be exploited for the conservation of cultural heritage. These nanostructures can be successfully applied without releasing toxic compounds, thus spreading their usability.

Microstructure and chemical composition of Roman orichalcum coins emitted after the monetary reform of Augustus (23 B.C.).

A collection of ancient Roman orichalcum coins, i.e., a copper-zinc alloy, minted under the reigns from Caesar to Domitianus, have been characterised using scanning electron microscopy (SEM-EDS) and electron microprobe analysis (EMPA). We studied, for the first time, coins emitted by Romans after the reforms of Augustus (23 B.C.) and Nero (63-64 A.D). These coins, consisting of asses, sestertii, dupondii and semisses, were analysed using non- and invasive analyses, aiming to explore microstructure, corrosive process and to acquire quantitative chemical analysis. The results revealed that the coins are characterized by porous external layers, which are affected by dezincification and decuprification processes. As pictured by the X-ray maps, the elemental distribution of Cu and Zn shows patterns of depletion that in some cases penetrate in deep up to 1 mm. The composition of the un-corroded nucleus is a Cu-Zn alloy containing up to 30% of Zn, typical of coins produced via cementation process.

Multi-technique characterisation of commercial alizarin-based lakes.

The characterization of ancient and modern alizarin-based lakes is a largely studied topic in the literature. Analytical data on contemporary alizarin-based lakes, however, are still poor, though of primary importance, since these lakes might be indeed present in contemporary and fake paintings as well as in retouchings. In this work we systematically investigate the chemical composition and the optical features of fifteen alizarin-based lakes, by a multi-analytical technique approach combining spectroscopic methods (i.e. Energy Dispersive X-ray Fluorescence Spectroscopy, EDXRF; Attenuated Total Reflectance Fourier-Transform Infrared Spectroscopy, ATR-FTIR; X-ray Powder Diffraction, XRD; UV induced fluorescence and reflectance spectroscopies) and chromatography (i.e. High-performance Liquid Chromatography coupled with a Photodiode Array Detector, HPLC-PDA). Most of the samples contain typical compounds from the natural roots of madder, as occurring in ancient and modern lakes, but in two samples (23600-Kremer-Pigmente and alizarin crimson-Zecchi) any anthraquinonic structures were identified, thus leading to hypothesize the presence of synthetic dyes. The detection of lucidin primeveroside and ruberythrique acid in some lakes suggest the use of Rubia tinctorum. One sample (23610-Kremer-Pigmente) presents alizarin as the sole compound, thereby revealing to be a synthetic dye. Moreover, gibbsite, alunite and kaolinite were found to be used as substrates and/or mordants. Visible absorption spectra of the anthraquinonic lakes show two main absorption bands at about 494-511nm and 537-564nm, along with a shoulder at about 473-479nm in presence of high amounts of purpurin. Finally, from the results obtained by UV induced fluorescence spectroscopy it is possible to figure out that, although it is commonly assumed that the madder lake presents an orange-pink fluorescence, the inorganic compounds, added to the recipe, could induce a quenching phenomenon or an inhibition of the fluorescence, as occurring in some commercial alizarin-based lakes.

Spectral Behavior of White Pigment Mixtures Using Reflectance, Ultraviolet-Fluorescence Spectroscopy, and Multispectral Imaging.

Reflectance spectroscopy, ultraviolet (UV)-fluorescence spectroscopy, and multispectral imaging have been widely employed for pigment identification on paintings. From ancient times to the present, lead white, zinc white, and titanium white have been the most important white pigments used for paintings and they are used as pigment markers for dating a work of art. The spectral behavior of these pigments is reported in several scientific papers and websites, but those of their mixtures are quite unknown. We present a combined nondestructive approach for identifying mixtures of lead white, zinc white, and titanium white as powder and dispersed in two different binder media (egg yolk and linseed oil) by using reflectance spectroscopy, spectrofluorimetry, multispectral reflectance and UV-fluorescence imaging. We propose a novel approach for mapping the presence of white pigments in paintings by false color images obtained from multispectral reflectance and UV-fluorescence images. We found that the presence of lead white mixed with either zinc white or titanium white is highly detectable. Zinc white mixed with lead white or titanium white can be identified due to its UV-fluorescence emission, whereas titanium white in association with lead white or zinc white is distinguishable by its reflectance spectral features. In most cases, the UV-fluorescence analyses also permit the recognition of the binder media in which the pigments are dispersed.