Natural based products for cleaning copper and copper alloys artefacts.

Copper alloys objects can deteriorate their conservation state through irreversible corrosion. Since in the cultural heritage field every artefact is unique and any loss irreplaceable, solutions for conservation are needed. Hence, there is the necessity to stop the corrosion process with a suitable cleaning and conservation process to avoid further degradation processes without changing its morphological aspect. Chelating solutions are commonly used in chemical cleaning, mainly sodium salts of ethylenediaminetetraacetic acid (EDTA). However, it is resistant to water purification procedures and is not biodegradable. The goal of this study was to see if applying an ecologically friendly chelating agent as an alternative to EDTA cleaning procedures for cultural heritage was suitable. In this study were chosen six natural-based chelators that could be a new green non-toxic alternative to EDTA in corrosion-inhibiting properties. They were tested for cleaning copper artefacts exposed to atmospheric environment in polluted areas. The study considered four amino acids, a glucoheptonate (CSA) and an industrial green chelator (GLDA). The effectiveness was tested on corrosion copper compounds and on laboratory corroded copper sheets. Finally, the cleaning efficacy was tested on four Roman coins and a modern copper painting. To define the cleaning efficacy, surface analytical investigations have been carried out by means ICP-OES, UV-VIS, µ-Raman, spectro-colorimetry, XRD and FTIR. Among the amino acids, alanine was the most effective, showing an unaltered noble patina and a good effective copper recovery from corrosion patinas.

Syntheses of APTMS-Coated ZnO: An Investigation towards Penconazole Detection.

Extrinsic chemiluminescence can be an efficient tool for determining pesticides and fungicides, which do not possess any intrinsic fluorescent signal. On this basis, (3-aminopropyl) trimethoxysilane (APTMS)-coated ZnO (APTMS@ZnO) was synthesized and tested as an extrinsic probe for the fungicide penconazole. Several synthetic routes were probed using either a one-pot or two-steps method, in order to ensure both a green synthetic pathway and a good signal variation for the penconazole concentration. The synthesized samples were characterized using X-ray diffraction (XRD), infrared (IR), Raman and ultraviolet-visible (UV-Vis) spectroscopy, scanning electron microscopy (SEM) imaging and associated energy-dispersive X-ray (EDX) analysis. The average size of the synthesized ZnO nanoparticles (NPs) is 54 ± 10 nm, in line with previous preparations. Of all the samples, those synthesized in two steps, at temperatures ranging from room temperature (RT) to a maximum of 40 °C, using water solvent (G-APTMG@ZnO), appeared to be composed of nanoparticles, homogeneously coated with APTMS. Chemiluminescence tests of G-APTMG@ZnO, in the penconazole concentration range 0.7-1.7 ppm resulted in a quenching of the native signal between 6% and 19% with a good linear response, thus indicating a green pathway for detecting the contaminant. The estimated detection limit (LOD) is 0.1 ± 0.01 ppm.

A Facile One-Pot Approach to the Fabrication of Nanocellulose-Titanium Dioxide Nanocomposites with Promising Photocatalytic and Antimicrobial Activity.

The combination of cellulosic materials and metal oxide semiconductors can provide composites with superior functional properties compared to cellulose. By using nanocellulose derived from agricultural waste, we propose a one-pot and environmentally friendly approach to the synthesis of nanocellulose-TiO2 (NC-TiO2) nanocomposites with peculiar photocatalytic activity and antibacterial effects. The as-prepared NC-TiO2 composites were fully characterized by different techniques, such as X-ray diffraction (XRD), µ-Raman, Fourier transform infrared spectroscopy (FTIR), thermogravimetry analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and diffuse reflectance spectroscopy (DRS). The results showed that well crystalline anatase TiO2 nanoparticles of about 5-6 nm were obtained. The photocatalytic activity in particular was evaluated by using methyl orange (MO) solution as a target pollutant at different pH values. It was found that all the tested NC-TiO2 nanocomposites showed stable photocatalytic activity, even after consecutive photocatalytic runs. In addition, NCT nanocomposites with higher TiO2 content showed degradation efficiency of almost 99% towards MO after 180 min of UV illumination. Finally, NC-TiO2 nanocomposites also showed intriguing antimicrobial properties, demonstrating to be effective against Gram-positive (Staphylococcus aureus, Bacillus subtilis) with 20-25 mm of inhibition zone and Gram-negative bacteria (Escherichia coli, Pseudomonas aeuroginosa) with 21-24 mm of inhibition zone, and fungi (Candida albicans) with 9-10 mm of inhibition zone.

A comprehensive strategy for exploring corrosion in iron-based artefacts through advanced Multiscale X-ray Microscopy.

The best strategy to tackle complexity when analyzing corrosion in iron artefacts is to combine different analytical methods. Traditional techniques provide effective means to identify the chemistry and mineralogy of corrosion products. Nevertheless, a further step is necessary to upgrade the understanding of the corrosion evolution in three dimensions. In this regard, Multiscale X-ray Microscopy (XRM) enables multi-length scale visualization of the whole object and provides the spatial distribution of corrosion phases. Herein, we propose an integrated workflow to explore corrosion mechanisms in an iron-nail from Motya (Italy) through destructive and non-destructive techniques, which permit the extraction of the maximum information with the minimum sampling. The results reveal the internal structure of the artefact and the structural discontinuities which lead the corrosion, highlighting the compositional differences between the tip and the head of the iron nail.

Evaluation of Long-Lasting Antibacterial Properties and Cytotoxic Behavior of Functionalized Silver-Nanocellulose Composite.

Materials possessing long-term antibacterial behavior and high cytotoxicity are of extreme interest in several applications, from biomedical devices to food packaging. Furthermore, for the safeguard of the human health and the environment, it is also stringent keeping in mind the need to gather good functional performances with the development of ecofriendly materials and processes. In this study, we propose a green fabrication method for the synthesis of silver nanoparticles supported on oxidized nanocellulose (ONCs), acting as both template and reducing agent. The complete structural and morphological characterization shows that well-dispersed and crystalline Ag nanoparticles of about 10-20 nm were obtained in the cellulose matrix. The antibacterial properties of Ag-nanocomposites (Ag-ONCs) were evaluated through specific Agar diffusion tests against E. coli bacteria, and the results clearly demonstrate that Ag-ONCs possess high long-lasting antibacterial behavior, retained up to 85% growth bacteria inhibition, even after 30 days of incubation. Finally, cell viability assays reveal that Ag-ONCs show a significant cytotoxicity in mouse embryonic fibroblasts.

Fabrication of packaging paper sheets decorated with alginate/oxidized nanocellulose­silver nanoparticles bio-nanocomposite.

Packaging is as important as the product itself because it is a crucial marketing and communication tool for business. Oxidized nanocellulose (ONC), extracted from agriculture residues of bagasse raw material using ecofriendly ammonium persulfate hydrolysis method, is used as support/reducing agent for the generation of silver nanoparticles (AgNPs) via photochemical procedure and reinforcing element in paper functionalization. The natural polymer, sodium alginate (SA) is exploited to enhance the binding of the ONC-AgNPs over cellulose fibers. The SA/ONC-AgNPs bio-nanocomposite is incorporated on paper matrix, which represents a more suitable choice respect to other substrates for its renewable, biocompatible, biodegradable, and cost-effective properties. Structural and antimicrobial evaluations show that the papers embedded with the SA/ONC-AgNPs possess good mechanical, thermal, barrier and antibacterial properties.

Microchemical, structural and mineralogical study of ancient Moroccan pyrometallurgical remains and data sharing through the support of a QGIS software.

The mining areas of the Middle Atlas, already inhabited in the Neolithic period, have been under the influences of different cultures, firstly Phoenician, then Punic or Ibero-Punic, Berber, Roman and finally Islamic. The impact of external cultures on the evolution and development of ancient metallurgy in the north-central Atlas region and the Southern Rift occurred since prehistoric times to Arab domination in the Middle Ages. This study proposes the development of an up-to-date protocol for archaeometallurgical investigation, based on the correlation between the chemical-physical analysis of the pyrometallurgical materials and the contextual systematic geoarchaeological excavations. The microchemical analysis has been carried out on opportunely selected pyrometallurgical materials, coming from different mining areas of the Middle Atlas regions in Morocco (Tabarouch for Cu and Aouam for Pb/Ag) in order to understand the evolution of the technological knowledge in archaeometallurgical work of local people. After that, the analytical results have been included in a Geographic Information System (GIS) software with the aim of creating an easily usable database that will support multidisciplinary research on the ancient metallurgical activities also with its future development and implementation. The GIS application could indeed correlate all the data coming from different extraction/work sites, present in the exploited mining veins. Furthermore, the GIS application is a starting point for an integrated study of the different mining archaeological sites in the Mediterranean basin proposing an innovative method of data exchange of archaeological, physical and geological chemical results.

Femtosecond-Laser Nanostructuring of Black Diamond Films under Different Gas Environments.

Irradiation of diamond with femtosecond (fs) laser pulses in ultra-high vacuum (UHV) conditions results in the formation of surface periodic nanostructures able to strongly interact with visible and infrared light. As a result, native transparent diamond turns into a completely different material, namely "black" diamond, with outstanding absorptance properties in the solar radiation wavelength range, which can be efficiently exploited in innovative solar energy converters. Of course, even if extremely effective, the use of UHV strongly complicates the fabrication process. In this work, in order to pave the way to an easier and more cost-effective manufacturing workflow of black diamond, we demonstrate that it is possible to ensure the same optical properties as those of UHV-fabricated films by performing an fs-laser nanostructuring at ambient conditions (i.e., room temperature and atmospheric pressure) under a constant He flow, as inferred from the combined use of scanning electron microscopy, Raman spectroscopy, and spectrophotometry analysis. Conversely, if the laser treatment is performed under a compressed air flow, or a N2 flow, the optical properties of black diamond films are not comparable to those of their UHV-fabricated counterparts.

Study of the Effect of Titanium Dioxide Hydrosol on the Photocatalytic and Mechanical Properties of Paper Sheets.

Different amounts of a stable aqueous TiO2 hydrosol were used to fabricate paper sheets having photocatalytic activity. The TiO2 hydrosol was prepared in aqueous medium using titanium butoxide as precursor and acetic acid as catalyst for the hydrolysis of titanium butoxide. An aging process at room temperature and atmospheric pressure was finally applied to obtain crystalline anatase TiO2 hydrosol. The effects of different TiO2 hydrosol loadings on the mechanical strength and barrier properties of modified paper sheets were investigated in detail. The photocatalytic behavior of TiO2-modified paper sheets was investigated as well using methylene blue (MB) as target pollutant.

Green synthesis of gold-chitosan nanocomposites for caffeic acid sensing.

In this work, colloidal gold nanoparticles (AuNPs) stabilized into a chitosan matrix were prepared using a green route. The synthesis was carried out by reducing Au(III) to Au(0) in an aqueous solution of chitosan and different organic acids (i.e., acetic, malonic, or oxalic acid). We have demonstrated that by varying the nature of the acid it is possible to tune the reduction rate of the gold precursor (HAuCl(4)) and to modify the morphology of the resulting metal nanoparticles. The use of chitosan, a biocompatible and biodegradable polymer with a large number of amino and hydroxyl functional groups, enables the simultaneous synthesis and surface modification of AuNPs in one pot. Because of the excellent film-forming capability of this polymer, AuNPs-chitosan solutions were used to obtain hybrid nanocomposite films that combine highly conductive AuNPs with a large number of organic functional groups. Herein, Au-chitosan nanocomposites are successfully proposed as sensitive and selective electrochemical sensors for the determination of caffeic acid, an antioxidant that has recently attracted much attention because of its benefits to human health. A linear response was obtained over a wide range of concentration from 5.00 × 10(-8) M to 2.00 × 10(-3) M, and the limit of detection (LOD) was estimated to be 2.50 × 10(-8) M. Moreover, further analyses have demonstrated that a high selectivity toward caffeic acid can be achieved without interference from catechin or ascorbic acid (flavonoid and nonphenolic antioxidants, respectively). This novel synthesis approach and the high performances of Au-chitosan hybrid materials in the determination of caffeic acid open up new routes in the design of highly efficient sensors, which are of great interest for the analysis of complex matrices such as wine, soft drinks, and fruit beverages.