Skip to main content
Log in

Identification of proteinaceous binding media for the polychrome terracotta army of Emperor Qin Shihuang by MALDI-TOF-MS

  • Article
  • Analytical Chemistry
  • Published:
Chinese Science Bulletin

Abstract

A proteinaceous binding media for the polychrome terracotta army of Emperor Qin Shihuang has been identified using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Methods for the preparation of the model samples and the elimination of interferences have been evaluated, as well as ageing processes. A method involving the complexation of EDTA in combination with dialysis was used to eliminate any interference in the polychrome layers taken from the historical samples. The model samples were aged by being buried in loess to replicate the ageing process of the historical samples as closely as possible. The optimum conditions for the extraction and subsequent enzymatic hydrolysis of the extracted protein were investigated. Under the optimized conditions, the “peptide mass fingerprints” of the proteinaceous binding media from the historical and model samples were determined by MALDI-TOF-MS. The results revealed that animal glue was used as the binding media for the polychrome layers of Emperor Qin Shihuang’s terracotta army. It also shows that animal glue used as binding media has a long history in China.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Museum of Emperor Qin Shihuang’s Terracotta Army (2004) The research reports of the Conservation Technology of the Polychromy of Qin Terracotta and Horses, Xi’an (in Chinese)

  2. The Research Group of the Conservation Technology of the Polychromy of Qin Terracotta and Horses (2005) Studies on the conservation technology of the polychromy of Qin Shihuang’s terracotta and horses. J Chin Lacq 24:7–16 (in Chinese)

    Google Scholar 

  3. Herm C (2001) Analysis of painting materials. In: Blänsdorf C, Emmerling E, Petzet M (eds) The terracotta army of the first Chinese Emperor Qin Shihuang. Bayerisches Landesamt für Denkmalpflege, München, pp 370–376

    Google Scholar 

  4. Bonaduce I, Blaensdorf C, Dietemann P et al (2008) The binding media of the polychromy of Qin Shihuang’s terracotta army. J Cult Herit 9:103–108

    Article  Google Scholar 

  5. Hynek R, Kuckova S, Hradilova J et al (2004) Matrix assisted laser desorption/ionization time-of-flight mass spectrometry as a tool for fast identification of protein binders in color layers of paintings. Rapid Commun Mass Spectr 18:1896–1900

    Article  Google Scholar 

  6. Tokarski C, Martin E, Rolando C et al (2006) Identification of proteins in renaissance paintings by proteomics. Anal Chem 78:1494–1502

    Article  Google Scholar 

  7. Kuckova S, Hynek R, Kodicek M (2007) Identification of proteinaceous binders used in artworks by MALDI–TOF mass spectrometry. Anal Bioanal Chem 388:201–206

    Article  Google Scholar 

  8. Kuckova S, Crhova M, Vankova L et al (2009) Towards proteomic analysis of milk proteins in historical building materials. Int J Mass Spectrom 284:42–46

    Article  Google Scholar 

  9. van der Werf ID, Calvano CD, Palmisano F et al (2012) A simple protocol for matrix assisted laser desorption ionization–time flight–mass spectrometry (MALDI–TOF–MS) analysis of lipids and proteins in single microsamples of paintings. Anal Chim Acta 718:1–10

    Article  Google Scholar 

  10. Ma Y, Lu Y, Zeng H et al (2001) Characterization of phosphopeptides from protein digests using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and nanoelectrospray quadrupole time-of-flight mass spectrometry. Rapid Commun Mass Spectrom 15:1693–1700

    Article  Google Scholar 

  11. An JJ, Yan HT (2013) The binding media of ancient polychromy by matrix-assisted laser desorption/ionization time-of-fight mass spectrometry (I). Chin Sci Bull (Chin Ver) 58:211–217 (in Chinese)

    Google Scholar 

  12. Yan HT, An JJ, Zhou T et al (2013) Analysis of proteinaceous binding media used in Tang Dynasty polychrome pottery by MALDI-TOF-MS. Chin Sci Bull 58:2932–2937

    Google Scholar 

  13. Jia SX (2009) Essential techniques for the peasantry (Qi Min Yao Shu). Chinese publishing house, Shanghai (in Chinese)

    Google Scholar 

  14. Wang SZ, Cao YX, Li H et al (2003) Comparison and analysis of physical and chemical components of eggs between cage-rearing and random-rearing chicken. Chin J Vet Sci 4:388–390 (in Chinese)

    Google Scholar 

  15. Bai J, Li Q (2012) Comparative studies on nutrient component of rural egg and ordinary egg. Poult Sci 9–11 (in Chinese)

  16. Shi XG, Wang SJ, Li FD et al (2007) Development and application of raw materials of animal protein feed. Chin J Anim Sci 43:46–50 (in Chinese)

    Google Scholar 

  17. Van Raamsdonk LWD, von Holst C, Baeten V et al (2007) New developments in the detection and identification of processed animal protein in feed. Anim Feed Sci Technol 133:63–83

    Article  Google Scholar 

  18. Dong XR (1986) A sketch of chicken raise in ancient China. Agric Archaeol 387–390 (in Chinese)

  19. Xie CX (1991) Egg and its utilization research. Agric Hist China 3:84–88 (in Chinese)

    Google Scholar 

  20. Colombini MP, Andreotti A, Bonaduce I et al (2010) Analytical strategies for characterizing organic plaint media using gas chromatography/mass spectrometry. Acc Chem Res 43:715–727

    Article  Google Scholar 

  21. Gautier G, Colombini MP (2007) GC/MS identification of proteins in wall painting samples: a fast clean-up procedure to remove copper-based pigment interferences. Talanta 73:95–102

    Article  Google Scholar 

  22. Bradford MM (1976) A rapid and sensitive method for the quantitative of microgram quantities of protein utilizing the principle of protein dye binding. Anal Biochem 72:248–254

    Article  Google Scholar 

  23. Wang YL (1987) Searching for the origin of animal glue (Dong wu jiao yuan yan tan bian,). Sci Technol Gelatin 3:148–151 (in Chinese)

    Google Scholar 

  24. Chen D (2003) Chinese adhesive and their application in remote ages. China Hist Mater Sci Technol 4:359–365 (in Chinese)

    Google Scholar 

  25. Wen RJ (2008) Transition and annotation of Kao gong ji. Chinese Ancient Books Publishing House, Beijing

    Google Scholar 

  26. Wei S, Ma Q, Schreiner M (2012) Scientific investigation of the paint and adhesive materials used in the Western Han dynasty polychromy terracotta army, Qinzhou, China. J Archaeol Sci 39:1628–1633

    Article  Google Scholar 

  27. Li S (1993) Preliminary understand of the binding media in Dunhuang wall paintings. Dunhuang Res 108–117 (in Chinese)

  28. Li S (1995) The quantitative analysis of the binding media in Dunhuang wall paintings. Dunhuang Res 29–46 (in Chinese)

  29. Su BM, Zhen BZF, Hu ZD et al (2005) HPLC analysis of binding media of pigments of wall paintings at Kizil grottoes. Dunhuang Res 57–61 (in Chinese)

  30. Wei S, Schreiner M, Rosenberg E et al (2011) Identification of the binding media in Tang Dynasty Chinese wall paintings by used Py–GC/MS and GC/MS techniques. J Int Conserv Sci 2:77–88

    Google Scholar 

Download references

Acknowledgments

This work was supported by the National Key Technology R&D Program of China (2010BAK67B12). The authors are very grateful to Prof. Zhijun Zhang for providing the photograph of the polychrome warrior of Qin Shihuang’s terracotta army.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Hongtao Yan.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 46 kb)

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yan, H., An, J., Zhou, T. et al. Identification of proteinaceous binding media for the polychrome terracotta army of Emperor Qin Shihuang by MALDI-TOF-MS. Chin. Sci. Bull. 59, 2574–2581 (2014). https://doi.org/10.1007/s11434-014-0372-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11434-014-0372-9

Keywords

Navigation