Optimization of Copper Stain Removal from Marble through the Formation of Cu(II) Complexes in Agar Gels.

Copper complexes with different ligands (ethylenediaminetetraacetic acid, EDTA, ammonium citrate tribasic, TAC, and alanine, ALA) were studied in aqueous solutions and hydrogels with the aim of setting the optimal conditions for copper stain removal from marble by agar gels, with damage minimization. The stoichiometry and stability of copper complexes were monitored by ultraviolet-visible (UV-Vis) spectroscopy and the symmetry of Cu(II) centers in the different gel formulations was studied by electron paramagnetic resonance (EPR) spectroscopy. Cleaning effectiveness in optimized conditions was verified on marble laboratory specimens through color variations and by determining copper on gels by inductively coupled plasma-mass spectrometry (ICP-MS). Two copper complexes with TAC were identified, one having the known stoichiometry 1:1, and the other 1:2, Cu(TAC)2, never observed before. The stability of all the complexes at different pH was observed to increase with pH. At pH 10.0, the gel's effectiveness in removing copper salts from marble was the highest in the presence of ALA, followed by EDTA, TAC, and pure agar gel. Limited damage to the marble surface was observed when gels with added EDTA and TAC were employed, whereas agar gel with ALA was determined to be the most efficient and safe cleaning material.

New Poly(ß-Cyclodextrin)/Poly(Vinyl Alcohol) Electrospun Sub-Micrometric Fibers and their Potential Application for Wastewater Treatments.

Cyclodextrin (CD)-based polymers are known to efficiently form molecular inclusion complexes with various organic and inorganic guest compounds. In addition, they also have a great potential as metal complexes because deprotonated hydroxyls can strongly bind metal ions under alkaline conditions. The range of environmental conditions for polycyclodextrin/metal ion complexation can be extended by the polymerization of CDs with polyacids. This article describes the preparation and characterization of a new type of poly(ß-cyclodextrin) (Poly-ßCD) sub-micrometric fibers and explores their potential as metal ion sorbents. A water-soluble hyper-branched ß-cyclodextrin polymer was blended with poly(vinyl alcohol) (PVA) and here used to improve the mechanical and morphological features of the fibers. Solutions with a different Poly-ßCD/PVA ratio were electrospun, and the fibers were cross-linked by a post-spinning thermal treatment at 160 °C to ensure non-solubility in water. The fiber morphology was analyzed by scanning electron microscopy (SEM) before and after the curing process, and physical-chemical properties were studied by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The capability of the insoluble cyclodextrin-based fibers to remove heavy metals from wastewaters was investigated by testing the adsorption of Cu2+ and Cd2+ using inductively coupled plasma-optical emission spectroscopy (ICP-OES). The results suggest that the poly(ß-cyclodextrin)/poly(vinyl alcohol) sub-micrometric fibers can complex metal ions and are especially effective Cu2+ sorbents, thus opening new perspectives to the development of fibers and membranes capable of removing both metal ions and organic pollutants.

Close to the diffraction limit in high resolution ATR FTIR mapping: demonstration on micrometric multi-layered art systems.

This paper is aimed at demonstrating the potentiality of high resolution Attenuated Total Reflection Fourier Transform Infrared micro-mapping (micro-ATR-FTIR) to reconstruct the images of micrometric multi-layered systems. This method can be an effective analytical alternative when the layer thickness requires high lateral resolution, and fluorescence or thermal effects prevent the deployment of conventional analytical techniques such as micro-Raman spectroscopy. This study demonstrates the high micro-ATR-FTIR setup performances in terms of lateral resolution, spectral quality and chemical image contrast using a new laboratory instrument equipped with a single element detector. The method has been first validated on mock-ups and then successfully applied on cross-sectional samples from real artworks: Leonardo da Vinci's mural painting, characterised by a few micrometers thin sequence of organic and inorganic layers, and an outdoor marble statue, with a complex sequence of decay products on its surface. This study paves the way to a new investigation modality of micrometric systems, combining high lateral resolution with excellent spectral quality, essential in the field of Cultural Heritage as well as in the wider area of materials and forensic sciences.

Determination of thickness of thin turbid painted over-layers using micro-scale spatially offset Raman spectroscopy.

We present a method for estimating the thickness of thin turbid layers using defocusing micro-spatially offset Raman spectroscopy (micro-SORS). The approach, applicable to highly turbid systems, enables one to predict depths in excess of those accessible with conventional Raman microscopy. The technique can be used, for example, to establish the paint layer thickness on cultural heritage objects, such as panel canvases, mural paintings, painted statues and decorated objects. Other applications include analysis in polymer, biological and biomedical disciplines, catalytic and forensics sciences where highly turbid overlayers are often present and where invasive probing may not be possible or is undesirable. The method comprises two stages: (i) a calibration step for training the method on a well characterized sample set with a known thickness, and (ii) a prediction step where the prediction of layer thickness is carried out non-invasively on samples of unknown thickness of the same chemical and physical make up as the calibration set. An illustrative example of a practical deployment of this method is the analysis of larger areas of paintings. In this case, first, a calibration would be performed on a fragment of painting of a known thickness (e.g. derived from cross-sectional analysis) and subsequently the analysis of thickness across larger areas of painting could then be carried out non-invasively. The performance of the method is compared with that of the more established optical coherence tomography (OCT) technique on identical sample set.This article is part of the themed issue 'Raman spectroscopy in art and archaeology'.

Portable Sequentially Shifted Excitation Raman spectroscopy as an innovative tool for in situ chemical interrogation of painted surfaces.

We present the first validation and application of portable Sequentially Shifted Excitation (SSE) Raman spectroscopy for the survey of painted layers in art. The method enables the acquisition of shifted Raman spectra and the recovery of the spectral data through the application of a suitable reconstruction algorithm. The technique has a great potentiality in art where commonly a strong fluorescence obscures the Raman signal of the target, especially when conventional portable Raman spectrometers are used for in situ analyses. Firstly, the analytical capability of portable SSE Raman spectroscopy is critically discussed using reference materials and laboratory specimens, comparing its results with other conventional high performance laboratory instruments (benchtop FT-Raman and dispersive Raman spectrometers with an external fiber optic probe); secondly, it is applied directly in situ to study the complex polychromy of Italian prestigious terracotta sculptures of the 16(th) century. Portable SSE Raman spectroscopy represents a new investigation modality in art, expanding the portfolio of non-invasive, chemically specific analytical tools.

Noninvasive analysis of thin turbid layers using microscale spatially offset Raman spectroscopy.

Here, we demonstrate, for the first time, the extension of applicability of recently developed microscale spatially offset Raman spectroscopy (SORS), micro-SORS, from the area of cultural heritage to a wider range of analytical problems involving thin, tens of micrometers thick diffusely scattering turbid layers. The method can be applied in situations where a high turbidity of layers prevents the deployment of conventional confocal Raman microscopy with its depth resolving capability. The method was applied successfully to detect noninvasively the presence of thin, highly turbid layers within polymers, wheat seeds, and paper. An invasive, cross sectional analysis confirmed the micro-SORS findings. Micro-SORS represents a new Raman imaging modality expanding the portfolio of noninvasive, chemically specific analytical tools.