Abstract
Indigoid dyes are well known as vat dyes. In their oxidized dichetonic form they are stable and insoluble in water, whereas in their reduced form, commonly known as leuco, they are soluble in water and able to be attached to fabric for dyeing purposes. These blue dyes are usually easily detectable in art objects by means of Raman spectroscopy by adopting for analyses a laser line at a high wavelength, such as a 785 nm diode laser. Unfortunately, in ancient artworks, that are often highly degraded, it is not always possible to collect high quality Raman spectra, which makes the analysis and identification of these compounds particularly challenging. In this work, we present a tailor-made methodology for the extraction and the recognition of indigoid dyes in works of art, which exploits the solubility of these compounds in their reduced form. Excellent Raman and surface enhanced Raman spectroscopy (SERS) spectra of indigo were acquired after micro-extraction on ancient and reference textiles, confirming the reliability of the presented procedure. Moreover, the methodology has been applied also for the extraction of the indigoid dye Tyrian purple on a reference textile, showing excellent results. This analytical method has been found to be extremely safe both for the reference textiles and the investigated ancient textiles, thus being a promising procedure for the selective analysis and detection of indigoid compounds in objects of artistic relevance.
Similar content being viewed by others
References
Clark RJH, Cooksey CJ, Daniels MAM, Withnall R (1993) Endeavour 7:191–1999
Bechtold T, Mussak R (2009) Handbook of Natural Colorants. John Wiley & Sons, New York
Cooksey CJ (2001) Molecules 6:736–769
Etters JN (1993) J Soc Dyers Color 109:251–255
Etters JN (1995) Textile Chem Color 27:17–22
Smith G, Clark RJH (2001) Rev Conserv 2:96–106
Miliani C, Romani A, Favaro G (1998) Spectrochim Acta A 54:581–588
Oakley LH, Fabian DM, Mayhew HE, Svoboda SA, Wustholz KL (2012) Anal Chem 84:8006–8012
Devièse T, Ribechini E, Baraldi P, Farago-Szekeres B, Duday H, Regert M, Colombini MP (2011) Anal Bioanal Chem 401:1739–1748
Lofrumento C, Ricci M, Platania E, Becucci M, Castellucci E (2013) J Raman Spectrosc 44:47–54
Platania E, Lombardi JR, Leona M, Shibayama N, Lofrumento C, Ricci M, Becucci M, Castellucci E (2014) J Raman Spectrosc 45:1133–1139
Leona M, Decuzzi P, Kubic TA, Gates G, Lombardi JR (2011) Anal Chem 83:3990–3993
Doherty B, Brunetti BG, Sgamellotti A, Miliani C (2011) J Raman Spectrosc 42:1932–1938
Doherty B, Presciutti F, Sgamellotti A, Brunetti B, Miliani C (2014) J Raman Spectrosc 45:1153–1159
Leona M, Stenger J, Ferloni E (2006) J Raman Spectrosc 37:981–992
Pozzi F, Lombardi JR, Bruni S, Leona M (2012) Anal Chem 84:3751–3577
Pozzi F, Lombardi JR, Leona M (2013) Heritage Sci. doi:10.1186/2050-7445-1-23
Chen K, Leona M, Vo-Dinh T (2007) Sensor Rev 27:109–120
Leona M (2009) Proc Natl Acad Sci USA 106:14757–14762
Cañamares MV, Garcia-Ramos JV, Domingo C, Sanchez-Cortes S (2006) Vibr Spectrosc 40:161–167
Cañamares MV, Garcia-Ramos JV, Domingo C, Sanchez-Cortes S (2004) J Raman Spectrosc 35:921–927
Jurasekova Z, Domingo C, Garcia-Ramos JV, Sanchez-Cortes S (2012) J Raman Spectrosc 43:1913–1919
Bruni S, Guglielmi V, Pozzi F (2011) J Raman Spectrosc 42:1267–1281
Whitney AV, Van Duyne RP, Casadio F (2006) J Raman Spectrosc 37:993–1002
Pozzi F, Shibayama N, Leona M, Lombardi JR (2013) J Raman Spectrosc 44:102–107
Corredor C, Teslova T, Canamares MV, Chen Z, Zhang J, Lombardi JR, Leona M (2009) Vibr Spectrosc 49:190–195
Shadi IT, Chowdhry BZ, Snowden MJ, Withnall R (2003) Spectrochim Acta A 59:2213–2220
Jurasekova Z, del Puerto E, Bruno J, Garcìa-Ramos JV, Sanchez-Cortes R, Domingo C (2010) J Raman Spectrosc 41:1455–1461
Pozzi F, Poldi G, Bruni S, De Luca E, Guglielmi V (2012) Archaeol Anthropol Sci 4:185–197
Bruni S, Guglielmi V, Pozzi F (2010) J Raman Spectrosc 41:175–180
Proietti N, Presciutti F, Di Tullio V, Doherty B, Marinelli AM, Provinciali B, Macchioni N, Capitani D, Miliani C (2011) Anal Bioanal Chem 399:3117–3131
Kurouski D, Zaleski S, Casadio F, Van Duyne RP, Shah NC (2014) JACS 136:8677–8684
Anzani M, Berzioli M, Cagna M, Campani E, Casoli A, Cremonesi P, Fratelli M, Rabbolini A, Riggiardi D (2008) Quaderno n.6/CESMAR7. Il Prato, Padova
Schweppe H (1997) In: FitzHugh EW (ed) Artists' pigments: a handbook of their history and characteristics. National Gallery of Art, Washington, DC
Lee PC, Meisel DJ (1982) J Phys Chem 86:3391–3395
Deguchi S, Tsudome M, Shen Y, Konishi S, Tsujii K, Ito S, Horikoshi K (2007) Soft Matter 3:1170–1175
Chui MM, Phillips RJ, McCarthy MJ (1995) J Colloid Interphase Sci 174:336–344
Sánchez del Río M, Picquart M, Haro-Poniatowski E, van Elslande E, Hugo Uc V (2006) J Raman Spectrosc 37:1046–1053
Tatsch E, Schrader B (1995) J Raman Spectrosc 26:467–473
Fiedler A, Baranska M, Schulz H (2011) J Raman Spectrosc 42:551–557
Acknowledgments
This work was supported by the Italian MIUR (grant no. 20100329WPF_007), the European Union (LASERLAB-Europe contract no.284464), and the Ente Cassa di Risparmio di Firenze (grant no. 2012-0849). Consorzio GRINT (http://www.consorziogrint.it) is gratefully acknowledged for providing the authors access to HIM.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
ESM 1
(PDF 668 kb)
Rights and permissions
About this article
Cite this article
Platania, E., Lofrumento, C., Lottini, E. et al. Tailored micro-extraction method for Raman/SERS detection of indigoids in ancient textiles. Anal Bioanal Chem 407, 6505–6514 (2015). https://doi.org/10.1007/s00216-015-8816-x
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00216-015-8816-x