The "Historical Materials BAG": A New Facilitated Access to Synchrotron X-ray Diffraction Analyses for Cultural Heritage Materials at the European Synchrotron Radiation Facility.

The European Synchrotron Radiation Facility (ESRF) has recently commissioned the new Extremely Brilliant Source (EBS). The gain in brightness as well as the continuous development of beamline instruments boosts the beamline performances, in particular in terms of accelerated data acquisition. This has motivated the development of new access modes as an alternative to standard proposals for access to beamtime, in particular via the "block allocation group" (BAG) mode. Here, we present the recently implemented "historical materials BAG": a community proposal giving to 10 European institutes the opportunity for guaranteed beamtime at two X-ray powder diffraction (XRPD) beamlines-ID13, for 2D high lateral resolution XRPD mapping, and ID22 for high angular resolution XRPD bulk analyses-with a particular focus on applications to cultural heritage. The capabilities offered by these instruments, the specific hardware and software developments to facilitate and speed-up data acquisition and data processing are detailed, and the first results from this new access are illustrated with recent applications to pigments, paintings, ceramics and wood.

The dependence of the spectroscopic properties of orcein dyes on solvent proticity: insights from theory and experiments.

The electronic spectral properties of α-hydroxy-orcein (α-HO), one of the main components of the orcein dye, have been extensively investigated in solvents of different proticity through UV-Vis spectrophotometry combined with DFT and TDDFT calculations. The results highlight the occurrence of an acid-base equilibrium between the neutral (absorption maximum at 475 nm) and the monoanionic (absorption maximum at 578 nm) forms of the molecule. The position of this equilibrium was found to be sensitively dependent on solvent proticity, solution concentration and pH. Quantum mechanical calculations support the rationalization of the experimental data, confirming the key role of the protic solvent in shifting the acid-base equilibrium, through the establishment of hydrogen bond interactions on specific functional groups of the dye. Both deprotonation and dye coordination with protic solvent molecules determine the reduction of the HOMO-LUMO energy gap (0.71 eV), that can be related with the bathochromic effect envisaged both experimentally (0.59 eV) and theoretically (0.50 eV).

Damages Induced by Synchrotron Radiation-Based X-ray Microanalysis in Chrome Yellow Paints and Related Cr-Compounds: Assessment, Quantification, and Mitigation Strategies.

Synchrotron radiation (SR)-based X-ray methods are powerful analytical tools for several purposes. They are widely used to probe the degradation mechanisms of inorganic artists' pigments in paintings, including chrome yellows (PbCr1-xSxO4; 0 ≤ x ≤ 0.8), a class of compounds often found in Van Gogh masterpieces. However, the high intensity and brightness of SR beams raise important issues regarding the potential damage inflicted on the analyzed samples. A thorough knowledge of the SR X-ray sensitivity of each class of pigment in the painting matrix is therefore required to find analytical strategies that seek to minimize the damage for preserving the integrity of the analyzed samples and to avoid data misinterpretation. Here, we employ a combination of Cr K-edge X-ray absorption near-edge structure spectroscopy, Cr-Kß X-ray emission spectroscopy, and X-ray diffraction to monitor and quantify the effects of SR X-rays on the stability of chrome yellows and related Cr compounds and to define mitigation strategies. We found that the SR X-ray beam exposure induces changes in the oxidation state and local coordination environment of Cr ions and leads to a loss of the compound's crystalline structure. The extent of X-ray damage depends on some intrinsic properties of the samples (chemical composition of the pigment and the presence/absence and nature of the binder). It can be minimized by optimizing the overall fluence/dose released to the samples and by working in vacuum and under cryogenic conditions.

Molecular Fluorescence Imaging Spectroscopy for Mapping Low Concentrations of Red Lake Pigments: Van†Gogh's Painting The Olive Orchard.

Vincent van Gogh used fugitive red lake pigments that have faded in some paintings. Mapping their distribution is key to understanding how his paintings have changed with time. While red lake pigments can be identified from microsamples, in situ identification and mapping remain challenging. This paper explores the ability of molecular fluorescence imaging spectroscopy to identify and, more importantly, map residual non-degraded red lakes. The high sensitivity of this method enabled identification of the emission spectra of eosin (tetrabromine fluorescein) lake mixed with lead or zinc white at lower concentrations than elemental X-ray fluorescence (XRF) spectroscopy used on account of bromine. The molecular fluorescence mapping of residual eosin and two carmine red lakes in van Gogh's The Olive Orchard is demonstrated and compared with XRF imaging spectroscopy. The red lakes are consistent with the composition of paint tubes known to have been used by van Gogh.

Role of the Relative Humidity and the Cd/Zn Stoichiometry in the Photooxidation Process of Cadmium Yellows (CdS/Cd1-x Znx S) in Oil Paintings.

Cadmium yellows (CdYs) refer to a family of cadmium sulfide pigments, which have been widely used by artists since the late 19th century. Despite being considered stable, they are suffering from discoloration in iconic paintings, such as Joy of Life by Matisse, Flowers in a blue vase by Van Gogh, and The Scream by Munch, most likely due to the formation of CdSO4 ⋅n H2 O. The driving factors of the CdYs degradation and how these affect the overall process are still unknown. Here, we study a series of oil mock-up paints made of CdYs of different stoichiometry (CdS/Cd0.76 Zn0.24 S) and crystalline structure (hexagonal/cubic) before and after aging at variable relative humidity under exposure to light and in darkness. Synchrotron radiation-based X-ray methods combined with UV-Vis and FTIR spectroscopy show that: 1) Cd0.76 Zn0.24 S is more susceptible to photooxidation than CdS; both compounds can act as photocatalysts for the oil oxidation. 2) The photooxidation of CdS/Cd0.76 Zn0.24 S to CdSO4 ⋅n H2 O is triggered by moisture. 3) The nature of alteration products depends on the aging conditions and the Cd/Zn stoichiometry. Based on our findings, we propose a scheme for the mechanism of the photocorrosion process and the photocatalytic activity of CdY pigments in the oil binder. Overall, our results form a reliable basis for understanding the degradation of CdS-based paints in artworks and contribute towards developing better ways of preserving them for future generations.

Photochemistry of Artists' Dyes and Pigments: Towards Better Understanding and Prevention of Colour Change in Works of Art.

The absorption of light gives a pigment its colour and its reason for being, but it also creates excited states, that is, new molecules with an energy excess that can be dissipated through degradation pathways. Photodegradation processes provoke long-term, cumulative and irreversible colour changes (fading, darkening, blanching) of which the prediction and prevention are challenging tasks. Of all the environmental risks that affect heritage materials, light exposure is the only one that cannot be controlled without any impact on the optimal display of the exhibit. Light-induced alterations are not only associated with the pigment itself but also with its interactions with support/binder and, in turn, are further complicated by the nature of the environmental conditions. In this Minireview we investigate how chemistry, encompassing multi-scale analytical investigations of works of art, computational modelling and physical and chemical studies contributes to improve our prediction of artwork appearance before degradation and to establish effective preventive conservation strategies.

Optimum Design Rules for CMOS Hall Sensors.

This manuscript analyzes the effects of design parameters, such as aspect ratio, doping concentration and bias, on the performance of a general CMOS Hall sensor, with insight on current-related sensitivity, power consumption, and bandwidth. The article focuses on rectangular-shaped Hall probes since this is the most general geometry leading to shape-independent results. The devices are analyzed by means of 3D-TCAD simulations embedding galvanomagnetic transport model, which takes into account the Lorentz force acting on carriers due to a magnetic field. Simulation results define a set of trade-offs and design rules that can be used by electronic designers to conceive their own Hall probes.

A Long-Distance RF-Powered Sensor Node with Adaptive Power Management for IoT Applications.

We present a self-sustained battery-less multi-sensor platform with RF harvesting capability down to -17 dBm and implementing a standard DASH7 wireless communication interface. The node operates at distances up to 17 m from a 2 W UHF carrier. RF power transfer allows operation when common energy scavenging sources (e.g., sun, heat, etc.) are not available, while the DASH7 communication protocol makes it fully compatible with a standard IoT infrastructure. An optimized energy-harvesting module has been designed, including a rectifying antenna (rectenna) and an integrated nano-power DC/DC converter performing maximum-power-point-tracking (MPPT). A nonlinear/electromagnetic co-design procedure is adopted to design the rectenna, which is optimized to operate at ultra-low power levels. An ultra-low power microcontroller controls on-board sensors and wireless protocol, to adapt the power consumption to the available detected power by changing wake-up policies. As a result, adaptive behavior can be observed in the designed platform, to the extent that the transmission data rate is dynamically determined by RF power. Among the novel features of the system, we highlight the use of nano-power energy harvesting, the implementation of specific hardware/software wake-up policies, optimized algorithms for best sampling rate implementation, and adaptive behavior by the node based on the power received.

Optical Communication among Oscillatory Reactions and Photo-Excitable Systems: UV and Visible Radiation Can Synchronize Artificial Neuron Models.

Neuromorphic engineering promises to have a revolutionary impact in our societies. A strategy to develop artificial neurons (ANs) is to use oscillatory and excitable chemical systems. Herein, we use UV and visible radiation as both excitatory and inhibitory signals for the communication among oscillatory reactions, such as the Belousov-Zhabotinsky and the chemiluminescent Orban transformations, and photo-excitable photochromic and fluorescent species. We present the experimental results and the simulations regarding pairs of ANs communicating by either one or two optical signals, and triads of ANs arranged in both feed-forward and recurrent networks. We find that the ANs, powered chemically and/or by the energy of electromagnetic radiation, can give rise to the emergent properties of in-phase, out-of-phase, anti-phase synchronizations and phase-locking, dynamically mimicking the communication among real neurons.

Lysis-on-chip of single target cells following forced interaction with CTLs or NK cells on a dielectrophoresis-based array.

Guiding the interaction of single cells acting as partners in heterotypic interactions (e.g., effectors and targets of immune lysis) and monitoring the outcome of these interactions are regarded as crucial biomedical achievements. In this study, taking advantage of a dielectrophoresis (DEP)-based Laboratory-on-a-chip platform (the DEPArray), we show that it is possible to generate closed DEP cages entrapping CTLs and NK cells as either single cells or clusters; reversibly immobilize a single virus-presenting or tumor cell within the chip at a selected position; move cages and their content to predetermined spatial coordinates by software-guided routing; force a cytotoxic effector to physically interact with a putative target within a secluded area by merging their respective cages; generate cages containing effector and target cells at predetermined E:T ratios; accurately assess cytotoxicity by real-time quantitation of the release kinetics of the fluorescent dye calcein from target cells (>50 lytic events may be tested simultaneously); estimate end points of calcein release within 16 min of initial E:T cell contact; simultaneously deliver Ab-based phenotyping and on-chip lysis assessment; and identify lytic and nonlytic E:T combinations and discriminate nonlytic effector phenotypes from target refractoriness to immune lysis. The proof of principle is provided that DEPArray technology, previously used to levitate and move single cells, can be used to identify highly lytic antiviral CTLs and tumor cells that are particularly refractory to NK cell lysis. These findings are of primary interest in targeted immunotherapy.

DFT/TDDFT investigation on the UV-vis absorption and fluorescence properties of alizarin dye.

The photophysical and photochemical properties of alizarin, a fluorescent organic red dye of the family of the anthraquinones, have been theoretically investigated by focusing our attention on its emission properties in relation to an excited-state internal proton transfers from the phenolic hydroxyl group to the carbonyl oxygen. The potential energy curve of the proton transfer in the first excited state has been computed in solvents of different polarity and the emission spectra of both tautomers simulated, including the vibronic effects, using the Franck-Condon approximation. Calculations performed by equilibrating the solvent with the excited-state geometry and electron density using a self-consistent procedure have led to interesting differences with respect to their linear response counterpart. The results obtained point out that, while the emission energy of alizarin is sensitive to solvent polarity, that of the proton-transfer tautomer is computed at similar wavelengths independently of the solvent. Comparison between computed and experimental data has allowed us to rationalize the alizarin double emission measured in non-polar solvents.

Non-Destructive and Non-Invasive Approaches for the Identification of Hydroxy Lead-Calcium Phosphate Solid Solutions ((PbxCa1-x)5(PO4)3OH) in Cultural Heritage Materials.

Lead-calcium phosphates are unusual compounds sometimes found in different kinds of cultural heritage objects. Structural and physicochemical properties of this family of materials, which fall into the hydroxypyromorphite-hydroxyapatite solid solution, or (PbxCa1-x)5(PO4)3OH, have received considerable attention during the last few decades for promising applications in different fields of environmental and material sciences, but their diagnostic implications in the cultural heritage context have been poorly explored. This paper aims to provide a clearer understanding of the relationship between compositional and structural properties of the peculiar series of (PbxCa1-x)5(PO4)3OH solid solutions and to determine key markers for their proper non-destructive and non-invasive identification in cultural heritage samples and objects. For this purpose, a systematic study of powders and paint mock-ups made up of commercial and in-house synthesized (PbxCa1-x)5(PO4)3OH compounds with a different Pb2+/Ca2+ ratio was carried out via a multi-technique approach based on scanning electron microscopy, synchrotron radiation-based X-ray techniques, i.e., X-ray powder diffraction and X-ray absorption near edge structure spectroscopy at the Ca K- and P K-edges, and vibrational spectroscopy methods, i.e., micro-Raman and Fourier transform infrared spectroscopy. The spectral modifications observed in the hydroxypyromorphite-hydroxyapatite solid solution series are discussed, by assessing the advantages and disadvantages of the proposed techniques and by providing reference data and optimized approaches for future non-destructive and non-invasive applications to study cultural heritage objects and samples.

Programmable interactions of functionalized single bioparticles in a dielectrophoresis-based microarray chip.

Manipulating single biological objects is a major unmet challenge of biomedicine. Herein, we describe a lab-on-a-chip platform based on dielectrophoresis (DEP). The DEParray is a prototypal version consisting of 320 × 320 arrayed electrodes generating >10,000 spherical DEP cages. It allows the capture and software-guided movement to predetermined spatial coordinates of single biological objects. With the DEParray we demonstrate (a) forced interaction between a single, preselected target cell and a programmable number of either microspheres or natural killer (NK) cells, (b) on-chip immunophenotypic discrimination of individual cells based on differential rosetting with microspheres functionalized with monoclonal antibodies to an inhibitory NK cell ligand (HLA-G), (c) on-chip, real-time (few minutes) assessment of immune lysis by either visual inspection or semiautomated, time-lapse reading of a fluorescent dye released from NK cell-sensitive targets, and (d) manipulation and immunophenotyping with limiting amounts (about 500) cells. To our knowledge, this is the first report describing a DEP-based lab-on-a-chip platform for the quick, arrayed, software-guided binding of individually moved biological objects, the targeting of single cells with microspheres, and the real-time characterization of immunophenotypes. The DEParray candidates as a discovery tool for novel cell:cell interactions with no prior (immuno)phenotypic knowledge.

Real-time gas mass spectroscopy by multivariate analysis.

Early and significant results for a real-time, column-free miniaturized gas mass spectrometer in detecting target species with partial overlapping spectra are reported. The achievements have been made using both nanoscale holes as a nanofluidic sampling inlet system and a robust statistical technique. Even if the presented physical implementation could be used with gas chromatography columns, the aim of high miniaturization requires investigating its detection performance with no aid. As a study case, in the first experiment, dichloromethane (CH2Cl2) and cyclohexane (C6H12) with concentrations in the 6-93 ppm range in single and compound mixtures were used. The nano-orifice column-free approach acquired raw spectra in 60 s with correlation coefficients of 0.525 and 0.578 to the NIST reference database, respectively. Then, we built a calibration dataset on 320 raw spectra of 10 known different blends of these two compounds using partial least square regression (PLSR) for statistical data inference. The model showed a normalized full-scale root-mean-square deviation (NRMSD) accuracy of [Formula: see text] and [Formula: see text] for each species, respectively, even in combined mixtures. A second experiment was conducted on mixes containing two other gasses, Xylene and Limonene, acting as interferents. Further 256 spectra were acquired on 8 new mixes, from which two models were developed to predict CH2Cl2 and C6H12, obtaining NRMSD values of 6.4% and 13.9%, respectively.

Fluorescence spectroscopy: a powerful technique for the noninvasive characterization of artwork.

After electronic excitation by ultraviolet or visible radiation, atoms and molecules can undergo thermal or radiative deactivation processes before relaxing to the ground state. They can emit photons with longer wavelengths than the incoming exciting radiation, that is, they can fluoresce in the UV-vis-near-infrared (NIR) range. The study of fluorescence relaxation processes is one of the experimental bases on which modern theories of atomic and molecular structure are founded. Over the past few decades, technological improvements in both optics and electronics have greatly expanded fluorimetric applications, particularly in analytical fields, because of the high sensitivity and specificity afforded by the methods. Using fluorimetry in the study and conservation of cultural heritage is a recent innovation. In this Account, we briefly summarize the use of fluorescence-based techniques in examining the constituent materials of a work of art in a noninvasive manner. Many chemical components in artwork, especially those of an organic nature, are fluorescent materials, which can be reliably used for both diagnostic and conservative purposes. We begin by examining fluorimetry in the laboratory setting, considering the organic dyes and inorganic pigments that are commonly studied. For a number of reasons, works of art often cannot be moved into laboratories, so we continue with a discussion of portable instruments and a variety of successful "field applications" of fluorimetry to works of cultural heritage. These examples include studies of mural paintings, canvas paintings, tapestries, and parchments. We conclude by examining recent advances in treating the data that are generated in fluorescence studies. These new perspectives are focused on the spectral shape and lifetime of the emitted radiation. Recent developments have provided the opportunity to use various spectroscopic techniques on an increasing number of objects, as well as the ability to fully characterize very small amounts of sample, either in a laboratory setting or on site. Thus, a new technological highway is open to scientists; it is still difficult to navigate but offers an enormous potential for investigating objects without touching them. Fluorescence spectroscopy is one of the most important of these techniques.

Photophysical properties of alizarin and purpurin Al(III) complexes in solution and in solid state.

The present study was undertaken to investigate the photophysical properties of the organic-metal compounds which are the main components of madder lake, one of the most commonly used and widespread organic pigments in painted artworks, from both geographic and historic points of view. Alizarin- and purpurin-Al(III) complexes were studied in solution and as powders. In solution, the chelate stoichiometry, their absorption and emission properties and the efficiency of their excited electronic state deactivation pathways have been determined. The two organic-metal compounds show relevant differences in terms of spectral features consisting of multiple peak (structured) absorption and emission spectra for the purpurin derivative and single broad bands (structureless) for the Al(III)-alizarin chelate. For both the investigated molecules, the chelation process induces a relevant increase of the emission quantum yields and lifetimes. The main differences between photophysical properties of the two metal complexes concern emission quantum yield and lifetime, which are both higher for purpurin chelate compared to alizarine chelate. Furthermore, interesting differences between the two metal complexes concerning the relative relevance of inter- and intra-molecular interaction involved in the mechanism of the excitation energy dissipation have been also highlighted. The knowledge of the determined parameters allows better understanding of the spectral behaviour in the solid state, thus providing a solid reference for the non-invasive characterisation and identification of madder lake on original artworks through its absorption and emission features.

Unveiling the composition of historical plastics through non-invasive reflection FT-IR spectroscopy in the extended near- and mid-Infrared spectral range.

The present research exploits the strengths of external reflection FT-IR spectroscopy to non-invasively study heritage plastic objects through inspection, for the first time, of the wide spectral range including the near- and mid-IR (12500-350 cm-1). Unlike most of previous works on historical plastic objects, reflection-mode spectra were not corrected for the unfamiliar surface reflection profiles to the more recognizable absorption-like band shapes. This avoided data misinterpretation due to ill-suited Kramers Krönig correction when volume reflection is also present or when highly absorbing IR compounds generate Reststrahlen bands. The inspection of the enlarged spectral range allowed the detection of fundamental, combination and overtone bands which provided reliable identification and semi-quantitative characterization of different polystyrene-based co-polymers. Furthermore the variation of the plastic optical properties across the explored spectral range allowed us to sample the plastic materials to different depths in the mid- and near-IR regions, so as to probe the chemistry at the surface and in the plastic bulk, respectively, in a non-invasive manner. This proved particularly useful to observe spectral markers of surface degradation occurring in historical ABS-based polymers.

Complexation of apigenin and luteolin in weld lake: a DFT/TDDFT investigation.

A DFT-TDDFT investigation on the aluminium complexation of apigenin and luteolin has been carried out. We have focused our attention on these hydroxyflavonoids, which are the main components of weld, one of the earliest natural dyestuff used in art. In particular, weld, upon complexation with Al(iii) forms a highly prized lake which has been widely used in medieval manuscripts and easel paintings for its rich yellow colour and transparency. The experimental spectra of apigenin and luteolin upon addition of increasing [Al(3+)] show a general red-shift of the lowest absorption bands of both flavonoids spectra, associated with the presence of two and three isosbestic points for apigenin and luteolin, respectively. The molecular geometries of all the Al-apigenin and -luteolin complexes have been optimized, followed by calculation of the formation Gibbs free energies and UV-vis absorption spectra. The comparison between the computed absorption spectra of the Al-flavonoid complexes and the experimental ones corresponding to various limit [Al(3+)] concentrations has been used to discriminate between the possible complexation modes as well as the stoichiometry ratio. We have thus been able to associate specific Al-apigenin (-luteolin) complexes with the experimental absorption spectra as a function of the [Al(3+)] concentration, thus providing insights into the aluminium complexation of these hydroxyflavonoids and most importantly into the weld lake composition.

Probing the chemistry of CdS paints in The Scream by in situ noninvasive spectroscopies and synchrotron radiation x-ray techniques.

The degradation of cadmium sulfide (CdS)-based oil paints is a phenomenon potentially threatening the iconic painting The Scream (ca. 1910) by Edvard Munch (Munch Museum, Oslo) that is still poorly understood. Here, we provide evidence for the presence of cadmium sulfate and sulfites as alteration products of the original CdS-based paint and explore the external circumstances and internal factors causing this transformation. Macroscale in situ noninvasive spectroscopy studies of the painting in combination with synchrotron-radiation x-ray microspectroscopy investigations of a microsample and artificially aged mock-ups show that moisture and mobile chlorine compounds are key factors for promoting the oxidation of CdS, while light (photodegradation) plays a less important role. Furthermore, under exposure to humidity, parallel/secondary reactions involving dissolution, migration through the paint, and recrystallization of water-soluble phases of the paint are associated with the formation of cadmium sulfates.

The exceptional near-infrared luminescence properties of cuprorivaite (Egyptian blue).

Cuprorivaite (CaCuSi(4)O(10), also known as Egyptian blue) exhibits an exceptionally high emission quantum efficiency in the near-infrared region (lambda(max) = 910 nm, Phi(EM) = 10.5%) and a long excited state lifetime (107 mus); these properties make it appealing for several applications in the fields of biomedical analysis, telecommunications and lasers.