Tert-butyldimethylsilyl chitosan synthesis and characterization by analytical ultracentrifugation, for archaeological wood conservation

The Oseberg ship is one of the most important archaeological testimonies of the Vikings. After excavation in 1904, the wooden gravegoods were conserved using alum salts. This resulted in extreme degradation of a number of the objects a hundred years later through acid depolymerisation of cellulose and lignin. The fragile condition of the artefacts requires a reconsolidation which has to be done avoiding water as solvent. We synthesized tert-butyldimethylsilyl (TBDMS) chitosan which is soluble in a 50:50 solution of ethyl acetate and toluene. Measurement of its molecular weight, to anticipate its penetration, provided a challenge as the density difference of the polymer and solvent was too small to provide adequate solute redistribution under a centrifugal field, so a two-stage process was implemented (i) determination of the weight-average molar mass of the aqueous soluble activated precursor, chitosan mesylate, Mw,mc using sedimentation equilibrium with the SEDFIT-MSTAR algorithm, and determination of the degree of polymerisation DP; (ii) measurement of the average degree of substitution DSTBDMS of the TBDMS group on each chitosan monosaccharide monomer unit using NMR, to augment the Mw,mc value to give the molar mass of the TBDMS-chitosan. For the preparation, we find Mw = 9.8 kg·mol−1, which is within the acceptable limit for penetration and consolidation of degraded wood. Future work will test this on archaeological wood from different sources

Novel application of liquid chromatography/mass spectrometry for the characterization of drying oils in art: Elucidation on the composition of original paint materials used by Edvard Munch (1863-1944)

Modern oil paints, introduced at the beginning of the 20th century, differ from those classically used in antiquity in their chemical and compositional features. The main ingredients were still traditional drying oils, often used in mixtures with less expensive oils and added with several classes of additives. Consequently, detailed lipid profiling, together with the study of lipid degradation processes, is essential for the knowledge and the conservation of paint materials used in modern and contemporary art.A multi-analytical approach based on mass spectrometry was used for the study of original paint materials from Munch's atelier, owned by the Munch Museum in Oslo. The results obtained in the analysis of paint tubes were compared with those obtained by characterizing a paint sample collected from one of the artist's sketches for the decoration of the Festival Hall of the University of Oslo (1909-1916).Py-GC/MS was used as screening method to evaluate the presence of lipid, proteic or polysaccaridic materials. GC/MS after hydrolysis and derivatization allowed us to determine the fatty acid profile of the paint tubes, and to evaluate the molecular changes associated to curing and ageing. The determination of the fatty acid profile is not conclusive for the characterization of complex mixtures of lipid materials, thus the characterization of the triglyceride profiles was performed using an analytical procedure based on HPLC-ESI-Q-ToF.This paper describes the first application of HPLC-ESI-Q-ToF for the acquisition of the triglyceride profile in a modern paint sample, showing the potentialities of liquid chromatography in the field of lipid characterization in modern paint materials. Moreover, our results highlighted that the application of this approach can contribute to address dating, authenticity and conservation issues relative to modern and contemporary artworks

Surveying silk fibre degradation by crystallinity determination: a study on the Tang-Dynasty silk treasure from Famen Temple, China

When Chinese archaeologists opened an unknown vault under the collapsed pagoda of Famen Temple near Xian (Shaanxi Province, NW China) in 1987, they found a vast amount of valuable silk textiles. The degraded textiles were part of a treasure comprising hundreds of artifacts deposited by Tang dynasty (ad 618–907) emperors as a gift to the temple.Run as a bilateral German-Chinese project, the Roemisch-Germanisches Zentralmuseum Mainz established a textile conservation laboratory in Shaanxi´s provincial capital Xian in 2001, joining numerous other laboratories that have existed there since the early 1990s.This preliminary study represents part of an ongoing investigation programme that accompanies the conservation work. The Tang dynasty silk is generally in a very poor state of preservation as a result of its long burial period. Large sections have only survived as an amorphous brown mass of fibre debris. Some parts are better preserved, however, offering the unique opportunity to study the whole range of degradation stages on ancient silks.This preliminary scientific investigation focuses on the determination of the silk fibres’ crystallinity and its relation to the ageing process. As we know from modern material, silk is mainly crystalline, albeit in a somewhat amorphous state. The methods of investigation used were X-ray diffraction (XRD) using synchrotron radiation, which is a new way to determine crystallinity of ancient silk fibres; and polarized Fourier transform infrared spectroscopy (FTIR) for the determination of crystallite orientation. Both methods were specifically devised to gain information on small single fibres

Virtual unwrapping of the Bispegata amulet, a multiple folded medieval amulet, by using neutron tomography

In recent decades, computed tomography (CT) combined with suitable image processing software has become a valuable tool to enable the reading of texts written on scrolls, which are fragile, damaged, or fused together, without physically unwrapping them. X-ray based computer tomography has successfully been used on scrolls made of soft materials such as papyrus and parchment. Although in few cases inscriptions on thin metal plates that have been rolled up and worn as amulets have been deciphered by using a high energy X-ray source, the readability of writings on of metal scrolls is limited by the high attenuation factor of this type of material. In this paper, we present for the first time the use of neutron tomography as an alternative to X-ray tomography for studying hidden inscriptions on folded metal objects. It is shown that the method overcomes the limitations of X-ray tomography caused by high attenuation of X-rays in lead objects. The inscription on the medieval Bispegata amulet, unearthed during excavations in Oslo's Old Town, has been read by using neutron tomography combined with VG Studio software. The amulet was made up of a thin lead sheet with an inscribed text, folded together into a rectangle. The inscription was runic, containing words of religious and magic meaning

Identification of green pigments and binders in late medieval painted wings from Norwegian churches

Green pigments in micro-samples taken from three late-medieval painted objects from Norwegian churches have been investigated with the aim to characterize their constituents and understand how they relate to damages observed in passages containing green paints. The cross-sections were analyzed by optical microscopy under visible and UV light, Scanning Electron Microscopy coupled with Energy Dispersive X-Ray Spectrometry and vibrational spectroscopies (Raman, ATR-FTIR). In addition, Gas Chromatography coupled with Mass Spectrometry was employed for the characterization of binding media, using a derivatization methodology recently developed for the detection of metal soaps in paint samples. This extensive characterization aided the identification of the individual constituents and the stratigraphy of green paints. It also builds the foundation for future ageing studies that can provide better insights into the mechanisms of the processes at stake in selective delamination of paints containing copper complexes.publishedVersio