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. 2019 Jun 12;24(12):2197.
doi: 10.3390/molecules24122197.

It's Only a Part of the Story: Analytical Investigation of the Inks and Dyes Used in the Privilegium Maius

Elisa Calà  1 , Fabio Gosetti  2 , Monica Gulmini  3 , Ilaria Serafini  4 , Alessandro Ciccola  5 , Roberta Curini  6 , Annalisa Salis  7 , Gianluca Damonte  8 , Kathrin Kininger  9 , Thomas Just  10 , Maurizio Aceto  11
Affiliations

It's Only a Part of the Story: Analytical Investigation of the Inks and Dyes Used in the Privilegium Maius

Elisa Calà et al. Molecules. .

Abstract

The Privilegium maius is one of the most famous and spectacular forgeries in medieval Europe. It is a set of charters made in the 14th century upon commitment by Duke Rudolf IV, a member of the Habsburg family, to elevate the rank and the prestige of his family. These five charters, now kept at the Österreichisches Staatsarchiv in Vienna, have been subjected to a thorough interdisciplinary study in order to shed light on its controversial story. The charters are composed of pergamenaceous documents bound to wax seals with coloured textile threads. The present contribution concerns the characterisation of the inks used for writing and of the dyes used to colour to the threads: Are they compatible with the presumed age of the charters? Though showing only a part of the whole story of the charters, dyes analysis could contribute in assessing their complex history from manufacturing to nowadays. The dyes were characterised with non-invasive in situ measurements by means of fibre optic (FORS) and with micro-invasive measurements by means of Surface Enhanced Raman Spectroscopy (SERS) and High-Performance Liquid Chromatography with Mass Spectrometry (HPLC-MS) analysis. The results showed that the threads of four of the charters (three dyed with madder, one with orchil) were apparently coloured at different dyeing stages, then re-dyed in the 19-20th century.

Keywords: Austria; Surface Enhanced Raman Spectroscopy (SERS); alizarin; dyes; fibre optic (FORS); forgery; inks; madder; manuscripts; orchil.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
The five charters constituting the Privilegium maius.
Figure 2
Figure 2
Fibre optic (FORS) spectra of the black inks.
Figure 3
Figure 3
(a) FORS spectra from purple threads; (b) molecular spectrofluorimetry with fibre optic (FOMF) spectra from purple threads.
Figure 4
Figure 4
(a) Surface Enhanced Raman Spectroscopy (SER) spectra from purple threads of AUR 1845 (top) and standard orchil (bottom); (b) SER spectra from purple threads of AUR 187 (top), purple threads of AUR 520 (middle) and standard alizarin (bottom).
Figure 5
Figure 5
Chromatogram from a purple thread.
Figure 6
Figure 6
Total ion current chromatogram of the purple threads of AUR 520.
Figure 7
Figure 7
Chromatogram from a yellow thread.
See this image and copyright information in PMC

References

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