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

1
Dipartimento di Scienze e Innovazione Tecnologica, Università degli Studi del Piemonte Orientale, viale T. Michel, 11-15121 Alessandria, Italy
2
Dipartimento di Chimica, Università degli Studi di Torino, via P. Giuria, 7-10125 Torino, Italy
3
Dipartimento di Chimica, Università di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Roma, Italy
4
Centre of Excellence for Biomedical Research (CEBR), Università degli Studi di Genova, viale Benedetto XV, 5-16132 Genova, Italy
5
Österreichisches Staatsarchiv, Haus-, Hof- und Staatsarchiv, Minoritenplatz, 1-1010 Wien, Austria
*
Author to whom correspondence should be addressed.
Molecules 2019, 24(12), 2197; https://doi.org/10.3390/molecules24122197
Received: 30 May 2019 / Revised: 10 June 2019 / Accepted: 10 June 2019 / Published: 12 June 2019
(This article belongs to the Special Issue Natural Dyes)
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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. View Full-Text
Keywords: alizarin; Austria; dyes; forgery; fibre optic (FORS); inks; madder; manuscripts; orchil; Surface Enhanced Raman Spectroscopy (SERS) alizarin; Austria; dyes; forgery; fibre optic (FORS); inks; madder; manuscripts; orchil; Surface Enhanced Raman Spectroscopy (SERS)
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).
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Calà, E.; Gosetti, F.; Gulmini, M.; Serafini, I.; Ciccola, A.; Curini, R.; Salis, A.; Damonte, G.; Kininger, K.; Just, T.; Aceto, M. It’s Only a Part of the Story: Analytical Investigation of the Inks and Dyes Used in the Privilegium Maius. Molecules 2019, 24, 2197.

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