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Analysis of natural red dyes (cochineal) in textiles of historical importance using HPLC and multivariate data analysis

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Abstract

A new analytical approach based on high-performance liquid chromatography with diode array detector (HPLC-DAD) and multivariate data analysis was applied and assessed for analyzing the red dye extracted from cochineal insects, used in precious historical textiles. The most widely used method of analysis involves quantification of specific minor compounds (markers), using HPLC-DAD. However, variation in the cochineal markers concentration, use of aggressive dye extraction methods and poor resolution of HPLC chromatograms can compromise the identification of the precise insect species used in the textiles. In this study, a soft extraction method combined with a new dye recovery treatment was developed, capable of yielding HPLC chromatograms with good resolution, for the first time, for historical cochineal-dyed textiles. After principal components analysis (PCA) and mass spectrometry (MS), it was possible to identify the cochineal species used in these textiles, in contrast to the accepted method of analysis. In order to compare both methodologies, 7 cochineal species and 63 historical cochineal insect specimens were analyzed using the two approaches, and then compared with the results for 15 historical textiles in order to assess their applicability to real complex samples. The methodology developed here was shown to provide more accurate and consistent information than the traditional method. Almost all of the historical textiles were dyed with Porphyrophora sp. insects. These results emphasize the importance of adopting the proposed methodology for future research on cochineal (and related red dyes). Mild extraction methods and HPLC-DAD/MSn analysis yield distinctive profiles, which, in combination with a PCA reference database, are a powerful tool for identifying red insect dyes.

In pursuit of a precious red dye! A new methodology has been developed for determining the precise cochineal dye used in historical textiles. Mild extraction methods and HPLC-DAD yield distinctive profiles that, in combination with a dye reference database based on PCA, creates a powerful tool for identifying the precise red dye used. Surprisingly, almost all of the historical textiles analysed were not dyed with American cochineal.

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Acknowledgements

We thank the following for financial support: Fundação para a Ciência e Tecnologia (FCT) and FEDER (POCI/QUI/099388/2008 and REDE/1502/REM/2005); for samples from the historical textiles: Maria Fernanda Passos Leite (Calouste Gulbenkian Museum, Lisbon, Portugal), Teresa Pacheco Pereira (Museu Nacional de Arte Antiga, Lisbon, Portugal) and Benjamin Bolour (B&Y Bolour Gallery, Los Angeles, CA, USA); for the historical cochineal specimens: Monique Simmonds and Mark Nesbitt (Royal Botanic Gardens, Kew, London, U.K.); and for cochineal insects: Douglas Miller (Agricultural Research Service, Systematic Entomology Laboratory, Beltsville, MD, USA), Ewa Simon (Faculty of Biology and Environmental Protection, University of Silesia, Katowice, Poland), Ferenc Kozár (Plant Protection Institute, Hungarian Academy of Sciences, Budapest, Hungary), Hassan-Ali Vahedi (College of Agriculture, Razi University, Kermanshah, Iran), Katarzyna Golan (Department of Entomology, University of Life Sciences, Lublin, Poland), Liberato Portillo (Botanical and Zoology Department, University of Guadalajara, Mexico) and Mónica González (Instituto Canario de Investigaciones Agrarias, Tenerife, Canary Islands).

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Authors and Affiliations

  1. Departmento de Conservação e Restauro, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516, Monte da Caparica, Portugal

    Ana Serrano & Micaela M. Sousa

  2. REQUIMTE, CQFB, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516, Monte da Caparica, Portugal

    Micaela M. Sousa

  3. CHAM (Centre for Overseas History), Faculdade de Ciências Sociais e Humanas, Universidade Nova de Lisboa and Universidade dos Açores, 1069-061, Lisboa, Portugal

    Jessica Hallett

  4. REQUIMTE, Departamento de Ciências Químicas, Faculdade de Farmácia, Universidade do Porto, 4099-030, Porto, Portugal

    João A. Lopes

  5. Centro de Química Estrutural, Complexo Interdisciplinar, Instituto Superior Técnico, Universidade Técnica de Lisboa, 1049-001, Lisboa, Portugal

    M. Conceição Oliveira

Authors
  1. Ana Serrano
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  2. Micaela M. Sousa
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  3. Jessica Hallett
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  4. João A. Lopes
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  5. M. Conceição Oliveira
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Corresponding authors

Correspondence to Micaela M. Sousa or Jessica Hallett.

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Figures with PCA scores (Figs. 1, 3B, C and 4A, B) were made using Matlab version 7.4 release 2007a (Mathworks, Natick, MA, USA). Figures 2, 3A and 4C were made with OriginPro 8 SR0 (OriginLab Corporation, Northampton, MA, USA).

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Serrano, A., Sousa, M.M., Hallett, J. et al. Analysis of natural red dyes (cochineal) in textiles of historical importance using HPLC and multivariate data analysis. Anal Bioanal Chem 401, 735–743 (2011). https://doi.org/10.1007/s00216-011-5094-0

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  • DOI: https://doi.org/10.1007/s00216-011-5094-0

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