Modelling the Interaction between Carboxylic Acids and Zinc Oxide: Insight into Degradation of ZnO Pigments.

Computational modelling applied to cultural heritage can assist the characterization of painting materials and help to understand their intrinsic and external degradation processes. The degradation of the widely employed zinc oxide (ZnO)-a white pigment mostly used in oil paints-leads to the formation of metal soaps, complexes of Zn ions and long-chain fatty acids coming from the degradation of the oil binder. Being a serious problem affecting the appearance and the structural integrity of many oil paintings, it is relevant to characterize the structure of these complexes and to understand the reaction pathways associated with this degradation process. Density functional theory (DFT) calculations were performed to investigate the adsorption of the acetate and acetic acid on relatively large ZnO clusters and the formation of Zn-acetate complexes. Carboxylic acids with longer alkyl chains were then investigated as more realistic models of the fatty acids present in the oil medium. In addition, DFT calculations using a periodic ZnO slab were performed in order to compare the obtained results at different levels of theory. Optimization calculations as well as the formation energies of the ZnO@carboxylate coupled systems and the thermodynamics leading to possible degradation products were computed. Our results highlight the potential for DFT calculations to provide a better understanding of oil paint degradation, with the aim of contributing to the development of strengthening and conservation strategies of paintings.

Single-sided NMR: a non-invasive diagnostic tool for monitoring swelling effects in paint films subjected to solvent cleaning.

During solvent cleaning of a painted surface, the control of solvent diffusion into the painting matrix is a primary concern for conservators. In this work, a comparative systematic study of solvent ingress and of the ensuing swelling phenomenon in paint films due to cleaning treatments was tackled using single-sided NMR. Specifically, the effects of a TAC aqueous solution (triammonium citrate in deionized water) applied in both free and gelled forms (by Klucel® G) on acrylic emulsion and vinyl-based model paints were evaluated. Notably, the NMR measurements (proton spin density depth profiles and transverse relaxation decays) collected before, during, and after these wet-cleaning tests proved that the use of the aqueous gel did not significantly minimize the penetration and the swelling action of water compared with the free solution. Furthermore, swelling effects associated with the use of an organic solvent (ligroin) were evaluated by NMR profilometry on varnished oil and egg-tempera paints. In this case, by comparing the depth profiles collected before and after the solvent treatments, a moderate paint swelling was observed followed by a width reduction of the paint films ascribable to the removed varnish layer.Overall, the reported NMR results reveal the analytical potentialities of the technique for a non-invasive assessment of the swelling effect of paint films subjected to cleaning (by water or an organic solvent), thereby providing an analytical method in support to the conservators' practice.

Revealing the Nature and Distribution of Metal Carboxylates in Jackson Pollock's Alchemy (1947) by Micro-Attenuated Total Reflection FT-IR Spectroscopic Imaging.

Protrusions, efflorescence, delamination, and opacity decreasing are severe degradation phenomena affecting oil paints with zinc oxide, one of the most common white pigments of the 20th century. Responsible for these dramatic alterations are the Zn carboxylates (also known as Zn soaps) originated by the interaction of the pigment and the fatty acids resulting from the hydrolysis of glycerides in the oil binding medium. Despite their widespread occurrence in paintings and the growing interest of the scientific community, the process of formation and evolution of Zn soaps is not yet fully understood. In this study micro-attenuated total reflection (ATR)-FT-IR spectroscopic imaging was required for the investigation at the microscale level of the nature and distribution of Zn soaps in the painting Alchemy by J. Pollock (1947, Peggy Guggenheim Collection, Venice) and for comparison with artificially aged model samples. For both actual samples and models, the role of AlSt(OH)2, a jellifying agent commonly added in 20th century paint tube formulations, proved decisive for the formation of zinc stearate-like (ZnSt2) soaps. It was observed that ZnSt2-like soaps first form around the added AlSt(OH)2 particles and then eventually grow within the whole painting stratigraphy as irregularly shaped particles. In some of the Alchemy samples, and diversely from the models, a peculiar distribution of ZnSt2 aggregates arranged as rounded and larger particles was also documented. Notably, in one of these samples, larger agglomerates of ZnSt2 expanding toward the support of the painting were observed and interpreted as the early stage of the formation of internal protrusions. Micro-ATR-FT-IR spectroscopic imaging, thanks to a very high chemical specificity combined with high spatial resolution, was proved to give valuable information for assessing the conservation state of irreplaceable 20th century oil paintings, revealing the chemical distribution of Zn soaps within the paint stratigraphy before their effect becomes disruptive.

Assessing Mechanochemical Properties of Acrylonitrile Butadiene Styrene (ABS) Items in Cultural Heritage Through a Multimodal Spectroscopic Approach.

A multimodal spectroscopic approach is proposed to correlate the mechanical and chemical properties of plastic materials in art and design objects, at both surface and subsurface levels, to obtain information about their conservation state and to monitor their degradation. The approach was used to investigate the photo-oxidation of acrylonitrile butadiene styrene (ABS), a plastic commonly found in many artistic and design applications, using ABS-based LEGO bricks as model samples. The modifications of the chemical and viscoelastic properties of ABS during photoaging were monitored by correlative Brillouin and Raman microspectroscopy (BRaMS), combined with portable and noninvasive broad-range external reflection infrared (IR) spectroscopy and nuclear magnetic resonance (NMR) relaxometry, directly applicable in museums. BRaMS enabled combined measurements of Brillouin light scattering and Raman spectroscopy in a microspectroscopic setup, providing for the coincident probe of the chemical and mechanical changes of ABS at the sample surface. NMR relaxometry allowed for noninvasive measurements of relaxation times and depth profiles which are directly related to the molecular mobility of the material. Complementary chemical information was acquired by external reflection IR spectroscopy. The simultaneous probe of the chemical and mechanical properties by this multimodal spectroscopic approach enabled us to define a decay model of ABS in terms of compositional changes and variation of stiffness and rigidity occurring with photodegradation. The knowledge acquired on LEGO samples has been used to rate the conservation state of ABS design objects noninvasively investigated by external reflection Fourier transform IR spectroscopy and NMR relaxometry offered by the MObile LABoratory (MOLAB) platform of the European Research Infrastructure of Heritage Science.

A Thermal Analytical Study of LEGO® Bricks for Investigating Light-Stability of ABS.

Acrylonitrile butadiene styrene (ABS) is a thermoplastic polymer widely used in several everyday life applications; moreover, it is also one of the most employed plastics in contemporary artworks and design objects. In this study, the chemical and thermal properties of an ABS-based polymer and its photo-degradation process were investigated through a multi-analytical approach based on thermal, mass spectrometric and spectroscopic techniques. LEGO® building blocks were selected for studying the ABS properties. First, the composition of unaged LEGO® bricks was determined in terms of polymer composition and thermal stability; then, the bricks were subjected to UV-Vis photo-oxidative-accelerated ageing for evaluation of possible degradation processes. The modifications of the chemical and thermal properties were monitored in time by a multi-technique approach aimed at improving the current knowledge of ABS photodegradation, employing pyrolysis online with gas chromatography and evolved gas analysis, coupled with mass spectrometric detection (Py-GC-MS and EGA-MS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and corroborated by external reflection FT-IR spectroscopy. The multimodal approach provided new evidence on the two-step degradation pathway proposed for ABS, defining molecular markers for polybutadiene oxidation and styrene-acrylonitrile depolymerization. Moreover, the results highlighted the feasibility of correlating accurate compositional and thermal data acquired by bulk techniques with external reflection FT-IR spectroscopy as a non-invasive portable tool to monitor the state of conservation of plastic museum objects in-situ.

Microscale mechanochemical characterization of drying oil films by in situ correlative Brillouin and Raman spectroscopy.

Correlative Brillouin and Raman microspectroscopy (BRaMS) is applied for the in situ monitoring of the chemical and physical changes of linseed oil during polymerization. The viscoelastic properties of the drying oil throughout the phase transition were determined by Brillouin light scattering (BLS) and joined to the Raman spectroscopic information about the chemical process responsible for the oil hardening. A comparative study was then performed on an oil mock-up containing ZnO, one of the most common white pigments used in cultural heritage. The intriguing outcomes open new research perspectives for a deeper comprehension of the processes leading to the conversion of a fluid binder into a dry adhering film. The description of both chemical and structural properties of the polymeric network and their evolution are the basis for a better understanding of oil painting degradation. Last, as a feasibility test, BRaMS was applied to study a precious microfragment from J. Pollock's masterpiece Alchemy.

Immunodetection of proteins in ancient paint media.

Diagnostic immunology is a powerful tool, widely used in clinical and biochemical laboratories for detecting molecules. In recent years, the technique has been adapted to materials sciences as a result of the extensive advances achieved in immunology. Today, many companies supply custom antibodies as well as new high-performance bioprobes for virtually any use. The idea of using immunodetection in the field of conservation science is not new. This analytical methodology is, in fact, particularly attractive for investigating biopolymers in painting materials; it is highly sensitive and selective with respect to the biological source of the target molecules. Among biopolymers, proteins have been widely used in the past as painting binders, adhesives, and additives in coating layers. An accurate assessment of these materials is necessary to obtain deeper insights into an artist's technique as well as to design proper restoration and conservation methods. In spite of the diagnostic potential offered by immunodetection-based techniques, some analytical drawbacks had, until recently, limited their use in routine applications in conservation science. In this Account, we highlight the most important results achieved in our research on the development of analytical methodologies based on the use of enzyme-linked immunosorbent assay (ELISA) and immuno-fluorescence microscopy (IFM) techniques for the highly sensitive and specific identification of proteins in artistic and archeological materials. ELISA and IFM offer two alternative analytical routes to this final goal: ELISA provides a fast, cost-effective, quantitative analysis of microsamples put in solution, whereas IFM combines the immunodetection of the targeted molecules with the characterization of their spatial distribution. The latter approach is of great value in the stratigraphic investigation of paintings. We discuss the limits and strengths of these methodologies in the context of the complex matrixes usually found in the investigated materials and the prolonged aging that they have undergone. Immunology is a relatively new technique in conservation science, providing a rich new field for innovation. We see two areas that are particularly ripe for future contributions. The commercial manufacture of antibodies specifically tailored for use in cultural heritage studies holds enormous potential. Moreover, the need for further refinement of detection systems in immuno-fluorescence techniques, especially the suppression of the autofluorescence background in painting materials, offers an abundance of opportunities for researchers. Immunology is a relatively new technique in conservation science, providing a rich new field for innovation.

Tracing the biological origin of animal glues used in paintings through mitochondrial DNA analysis.

We report the development of a suitable protocol for the identification of the biological origin of binding media on tiny samples from ancient paintings, by exploitation of the high specificity and high sensitivity offered by the state-of-the art DNA analysis. In particular, our aim was to molecularly characterize mitochondrial regions of the animal species traditionally employed for obtaining glues. The model has been developed using aged painting models and then tested to analyze the organic components in samples from the polychrome terracotta Madonna of Citerna by Donatello (1415-1420), where, by GC-MS and FTIR spectroscopy, animal glues and siccative oils were identified. The results obtained are good in terms of both sensibility and specificity of the method. First of all, it was possible to confirm that Donatello used animal glue for the preparation of the painted layers of the Madonna of Citerna and, specifically, glue derived from Bos taurus. Data obtained from sequencing confirm that each sample contains animal glue, revealing that it was mostly prepared from two common European taurine lineages called T2 and T3. There is one remarkable exception represented by one sample which falls into a surviving lineage of the now extinct European aurochs.

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.

An integrated analytical study of crayons from the original art materials collection of the MUNCH museum in Oslo.

Among the artists' materials of the nineteenth century, pastel crayons merit scientific interest since their early commercial formulations are mostly unknown and, until now, have been considerably less studied with respect to other contemporary painting materials. In this framework, research herein reports the results of a comprehensive multi-analytical study of 44 pastel crayons of two recognized brands (LeFranc and Dr. F. Schoenfeld) from the Munch museum collection of original materials belonging to Edvard Munch. The integrated use of complementary spectroscopic and hyphenated mass-spectrometry techniques allowed the compositional profiles of the crayons to be traced providing the identification of the inorganic and organic pigments, the fillers/extenders and the binders. All crayons resulted to be oil- based and the binder was identified to be a mixture of a drying oil (safflower or linseed oil), palm oil or Japan wax and beeswax. Among others, pigments such as ultramarine, chrome yellows, Prussian blue, manganese violet, viridian and madder lake have been identified. A significant alignment in formulations of the brands was observed with the only exception of the greens which showed distinctive pigment and filler compositions. The analytical information provided for these commercial artists' materials will be of great interest for academia, museum and other institutions hosting art collections dating from the same period and it will be used by the Munch museum to draw proper conservation strategies of its own artwork collections.

Synchrotron radiation Ca K-edge 2D-XANES spectroscopy for studying the stratigraphic distribution of calcium-based consolidants applied in limestones.

In Heritage Science, the evaluation of stone consolidation treatments by investigating the nature of in situ newly formed products and their penetration depth within the consolidated matrix is a grand challenge. A number of analytical methods have been proposed, but, currently, most of them are not able to supply a full overview of the spatial, structural and compositional information of the newly formed crystalline and amorphous phases with a submicrometric lateral resolution. Here, we examined, the capabilities of synchrotron radiation (SR)-based two-dimensional X-ray absorption near-edge structure (2D-XANES) spectroscopy at Ca K-edge for determining the structural and compositional properties of the compounds formed after the application of a calcium acetoacetate-based consolidant on a porous carbonatic stone (limestone) and for investigating their stratigraphic distribution at the submicrometric scale length. We evaluated advantages and drawbacks of three Ca K-edge 2D-XANES-based approaches: (i) transmission mode full-field-XANES (FF-XANES) imaging; (ii) micro-X-ray fluorescence (µ-XRF) mapping above the Ca K-edge combined with the acquisition of XRF mode µ-XANES spectra at a limited number of spots; (iii) full-spectral µ-XANES (FS µ-XANES) mapping in XRF mode and its variant called selectively induced X-ray emission spectroscopy (SIXES) mapping. Overall, Ca K-edge 2D-XANES spectroscopy provided accurate qualitative and semi-quantitative information on the newly formed calcium carbonates (i.e., amorphous calcium carbonate, vaterite and calcite) and their stratigraphic distribution at the submicrometric scale, thus opening a new scenario to study the carbonatation process of calcium-based consolidants in limestones.

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.

Proteomic strategies for the identification of proteinaceous binders in paintings.

The identification of proteinaceous components in paintings remains a challenging task for several reasons. In addition to the minute amount of sample available, complex and variable chemical composition of the paints themselves, possible simultaneous presence of several binders and contaminants, and degradation of the original materials due to aging and pollution are complicating factors. We proposed proteomic strategies for the identification of proteins in binders of paintings that can be adapted to overcome the requirements and difficulties presented by specific samples. In particular, we worked on (1) the development of a minimally invasive method based on the direct tryptic cleavage of the sample without protein extraction; (2) the use of microwave to enhance the enzymatic digestion yield, followed by the analysis of the peptide mixtures by nanoLC-MS/MS with electrospray ionization (ESI). Moreover, as an additional tool to tackle the problem of contaminating proteins, we exploited the possibility of generating an exclusion list of the mass signals that in a first run had been fragmented and that the mass spectrometer had to ignore for fragmentation in a subsequent run. The methods, tested on model samples, allowed the identification of milk proteins in a sample from paintings attributed to Cimabue and Giotto, thirteenth-century Italian masters, decorating the vaults of the upper church in the Basilica of St. Francis in Assisi, Italy.

Combined crossed molecular beam and theoretical studies of the N(2D) + CH4 reaction and implications for atmospheric models of Titan.

The dynamics of the H-displacement channel in the reaction N((2)D) + CH(4) has been investigated by the crossed molecular beam (CMB) technique with mass spectrometric detection and time-of-flight (TOF) analysis at five different collision energies (from 22.2 up to 65.1 kJ/mol). The CMB results have identified two distinct isomers as primary reaction products, methanimine and methylnitrene, the yield of which significantly varies with the total available energy. From the derived center-of-mass product angular and translational energy distributions the reaction micromechanisms, the product energy partitioning and the relative branching ratios of the competing reaction channels leading to the two isomers have been obtained. The interpretation of the scattering results is assisted by new ab initio electronic structure calculations of stationary points and product energetics for the CH(4)N ground state doublet potential energy surface. Differently from previous theoretical studies, both insertion and H-abstraction pathways have been found to be barrierless at all levels of theory employed in this work. A comparison between experimental results on the two isomer branching ratio and RRKM estimates, based on the new electronic structure calculations, confirms the highly nonstatistical nature of the N((2)D) + CH(4) reaction, with the production of the CH(3)N isomer dominated by dynamical effects. The implications for the chemical models of the atmosphere of Titan are discussed.

Immunochemical Methods Applied to Art-Historical Materials: Identification and Localization of Proteins by ELISA and IFM.

Despite the large diffusion of natural organic substances in art-historical materials, their characterization presents many challenges due to the chemical complexity and instability with respect to degradation processes. Among natural products, proteins have been largely used in the past as binders but also as adhesives or additives in coating layers. Nevertheless, biological identification of proteins in art-historical objects is one of the most recent achievements obtained in heritage science thanks to the development of specifically tailored bio-analytical strategies. In the context of this active emerging discipline, immunological methods stand out for sensitivity, specificity and versatility for both protein recognition and localization in micro-samples. Furthermore, the growing use of immunological techniques for advanced diagnostics and clinical applications ensures continuous improvement in their analytical performance. Considering such, this review provides an overview of the most recent applications of enzyme linked immunosorbent assay and immunofluorescence microscopy techniques in the field of heritage materials. Specifically, the main strengths and potentials of the two techniques as well as their limits and drawbacks are presented and discussed herein.

Non-invasive chemical and phase analysis of Roman bronze artefacts from Thamusida (Morocco).

A repertory of Roman military bronze equipment (1st- 3rd century AD) found at the archaeological site of Thamusida (Rabat, Morocco) was analysed by non-destructive X-ray fluorescence and time of flight neutron diffraction (ToF-ND). Most objects are made of leaded alloys, where copper is combined with tin and/or zinc and, in six cases, to arsenic as well. A mixed technology was employed, making a limited use of "pure" semi-finished materials if compared with the large utilization of recycled materials (brass and bronze).

The application of in situ mid-FTIR fibre-optic reflectance spectroscopy and GC-MS analysis to monitor and evaluate painting cleaning.

The development of non-invasive methodologies and portable instrumentation for in situ studies has been subject to great research and development in recent years in the field of conservation science. Despite such interest, very few reported studies employ these versatile techniques in the monitoring of cleaning treatments. This paper describes the application of mid-FTIR fibre-optic reflectance spectroscopy to monitor and evaluate the cleaning treatment of an oil painting using the chelating agent, triammonium citrate, a task undertaken in close collaboration with the painting conservator. Results obtained on site verify the removal of calcium oxalate and an organic component from the surface of the painting, later identified as a terpenic varnish. The subsequent, in laboratory FTIR and GC-MS analysis of the cotton swabs employed during the cleaning treatment acts as an additional non-invasive manner to support the results obtained in situ by mid-FTIR spectroscopy and to better understand the mechanism of the chosen cleaning agent.

Quantum effects in the differential cross Ssctions for the insertion reaction N(2D) + H2.

The quantum (QM) scattering theory has been difficult to apply to the family of insertion reactions and the approximate quasiclassical trajectory (QCT) method or statistical calculations were mostly applied. In this Letter, we compare the experimental differential cross sections for the title insertion reaction with the results of QM and QCT calculations on an ab initio potential energy surface. The QM results reproduce well the crossed beam experiment, while a small, but significant, difference in the QCT ones points to quantum effects, possibly the occurrence of tunneling through the combined potential and centrifugal barrier.