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Applied Photochemistry pp 499–530Cite as

Photochemistry for Cultural Heritage

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Part of the book series: Lecture Notes in Chemistry ((LNC,volume 92))

Abstract

Why do certain ancient natural dyes, such as indigo, preserve their colour so well while others, like brazilein, seem to degrade much faster? And how did mauveine change the world of colour? Will modern binding media, as vinyl paints, perform as well as a medieval tempera? Will it be possible to predict their durability? Photochemistry can answer many important questions about materials’ stability, providing new tools for the conservation of treasured artworks.

In this chapter, photochemistry emerges as an important contribution to the understanding of those complex processes, providing fascinating insights into a world of colour and light.

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Notes

  1. 1.

    The Mediterranean purple molluscs, Murex brandaris, Murex trunculus and Purpura haemastoma, have recently been renamed Bolinus brandaris, Hexaplex trunculus and Stramonita haemastoma, respectively, with the result that Murex and Purpura had disappeared from the name, and with it the memory of their importance as historic dyes was cancelled

  2. 2.

    Merocyanines structures, even with 6 conjugated double bonds, display an absorption wavelength maximum of only 510 nm (with a shift of 90–100 nm compared to indigo); see Fig. 13.5.

  3. 3.

    It will be useful to describe a dye as a two constituent system: the chromophore and the auxochrome. The chromophore group is responsible for basic colour, whereas the auxochromes allow the “enrichment” of the colour. Dilthey and Wizinger extended this concept defining the chromophore as an electron accepting group and the auxochromes as electron donating, linked to each other by conjugated bonds. This gave rise to the concept of the donor/acceptor dye type.

  4. 4.

    For the water soluble 5,5′-disulfonate derivative of indigo, indigocarmine, in DMF, the keto form is instantaneously formed with an intermolecular rate constant of ~1.4 × 1011 s−1 (by proton transfer to the solvent), whereas in methanol it is ~1.2 × 1011 s−1, making it more likely to be intramolecular.

  5. 5.

    Microspectrofluorimetry was used to analyze the red chromophores and SEM-EDX screening enabled to confirm the use of aluminium ion, Al3+, as a mordant and also to conclude that all the red samples studied were made of camelid fibers. Emission and excitation spectra were obtained in a 30 μm spot. The fluorophores were identified by comparing their spectra with those from historical reconstructions assembled in a database. In the Paracas and Nasca textiles, dated from 200 B.C. to A.D.1476, purpurin and pseudopurpurin were the red dyes used. Carminic acid was detected in textiles dated close to the Inca Empire, A.D. 1000–1476 [31].

  6. 6.

    This research was launched within the master thesis of Rita Araújo and Tatiana Vitorino

    - Rita Araújo, Os Livros de Horas (séc. XV) na colecção do Palácio Nacional de Mafra: estudo e conservação, 5 December 2012, [http://hdl.handle.net/10362/9329].

    - Tatiana Vitorino, A Closer Look at Brazilwood and its Lake Pigments, 5 December 2012, [http://run.unl.pt/bitstream/10362/10179/1/Vitorino_2012.pdf].

  7. 7.

    Colour coordinates for the brazilein-Al3+ complex, on filter paper: L* = 89, a* = 15, b* = 4.

  8. 8.

    Poly(vinyl acetate), PVAc (Fig. 13.12), was introduced in the market in 1928, and it has been widely used for household paints and adhesives in the form of aqueous emulsions.

  9. 9.

    Only soluble in organic media.

  10. 10.

    For all samples, Gaussian decomposition of the spectra in the carbonyl region (c.a. 1840–1660 cm−1) as well as the δCH3/C=O and νC-O/C=O ratios (absorption and peak area) show less than 5.5 % variations upon irradiation, indicating that the photochemical reactions involving the carbonyl group, if present, are still not relevant as detected by IR.

  11. 11.

    As no relevant weight losses relating to the release of volatiles are found, the number of scissions per chain, defined as S = Mn 0(1-x)/Mn t – 1, where Mn is the number average molecular weight before (Mn 0) and after irradiation (Mnt), and x is the fraction of volatilized polymer, may be calculated through the simplified expression.

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Authors and Affiliations

  1. LAQV-REQUIMTE, Department of Conservation and Restoration and Department of Chemistry, Faculty of Science and Technology, Universidade NOVA de Lisboa, Lisbon, Portugal

    Maria João Melo, Joana Lia Ferreira & António Jorge Parola

  2. CQC, Department of Chemistry, University of Coimbra, 3004-535, Rua Larga, Coimbra, Portugal

    João Sérgio Seixas de Melo

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  1. Maria João Melo
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  2. Joana Lia Ferreira
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  4. João Sérgio Seixas de Melo
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Correspondence to Maria João Melo .

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Editors and Affiliations

  1. Dipartimento di Chimica "Giacomo Ciamician", Università di Bologna, Bologna, Italy

    Giacomo Bergamini

  2. Dipartimento di Chimica "Giacomo Ciamician", Università di Bologna, Bologna, Italy

    Serena Silvi

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Melo, M.J., Ferreira, J.L., Parola, A.J., de Melo, J.S.S. (2016). Photochemistry for Cultural Heritage. In: Bergamini, G., Silvi, S. (eds) Applied Photochemistry. Lecture Notes in Chemistry, vol 92. Springer, Cham. https://doi.org/10.1007/978-3-319-31671-0_13

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