Advertisement

Analytical and Bioanalytical Chemistry

, Volume 402, Issue 4, pp 1551–1557 | Cite as

Solid-state and unilateral NMR study of deterioration of a Dead Sea Scroll fragment

  • A. MasicEmail author
  • M. R. Chierotti
  • R. Gobetto
  • G. Martra
  • I. Rabin
  • S. Coluccia
Original Paper

Abstract

Unilateral and solid-state nuclear magnetic resonance (NMR) analyses were performed on a parchment fragment of the Dead Sea Scroll (DSS). The analyzed sample belongs to the collection of non-inscribed and nontreated fragments of known archaeological provenance from the John Rylands University Library in Manchester. Therefore, it can be considered as original DSS material free from any contamination related to the post-discovery period. Considering the paramount significance of the DSS, noninvasive approaches and portable in situ nondestructive methods are of fundamental importance for the determination of composition, structure, and chemical–physical properties of the materials under study. NMR studies reveal low amounts of water content associated with very short proton relaxation times, T 1, indicating a high level of deterioration of collagen molecules within scroll fragments. In addition, 13C cross-polarization magic-angle-spinning (CPMAS) NMR spectroscopy shows characteristic peaks of lipids whose presence we attribute to the production technology that did not involve liming. Extraction with chloroform led to the reduction of both lipid and protein signals in the 13C CPMAS spectrum indicating probable involvement of lipids in parchment degradation processes. NMR absorption and relaxation measurements provide nondestructive, discriminative, and sensitive tools for studying the deterioration effects on the organization and properties of water and collagen within ancient manuscripts.

Fig

The state of deterioration of a Dead Sea scroll fragment was studied by means of 1H and 13C solid state NMR and proton T 1 relaxation measurements

Keywords

Dead Sea Scrolls Collagen deterioration Solid-state NMR Unilateral NMR 

Notes

Acknowledgments

The authors are grateful to the Piedmont Region for financial support. This work was performed as part of the EU IDAP (Improved Damage Assessment of Parchment, EVK4-2001-00061). We would like to thank Prof. G. Della Gatta, Dr. E. Badea, Dr. M. Odlyha, and Dr. R. Larsen for helpful discussions and support of this research. AM is grateful for the support by the Alexander von Humboldt Foundation and the Max Planck Society in the framework of the Max Planck Research Award funded by the Federal Ministry of Education and Research.

References

  1. 1.
    Temple scroll columns II-V, Report on the treatment in the laboratory of the Israel Antiquities Authority (2005). The Shrine of the BookGoogle Scholar
  2. 2.
    Boyd-Alkalay E, Libman E (1998) Preserving the Dead Sea Scrolls and Qumran Artifacts. In: Peter WF, Vanderkam JC (eds) The Dead Sea Scrolls after fifty years. Brill, Leiden, pp 535–544Google Scholar
  3. 3.
    Poole JB, Reed R (1962) The preparation of leather and parchment by the Dead Sea Scrolls community. Technol Cult 3:1–36Google Scholar
  4. 4.
    Kennedy CJ, Wess TJ (2003) The structure of collagen within parchment—a review. Restaur-Int J Preserv Libr Arch Mater 24(2):61–80Google Scholar
  5. 5.
    Kronick PL, Buechler PR (1986) Fiber orientation in calfskin by laser light scattering of X-ray diffraction and quantitative relation to mechanical properties. J Am Leather Chem Assoc 81:221–231Google Scholar
  6. 6.
    Purlslow PP, Wess TJ, Hukins DWL (1998) J Exp Biol 201:135–142Google Scholar
  7. 7.
    Fratzl P, Fratzl-Zelman N, Klaushofer K (1993) Biophys J 63:260Google Scholar
  8. 8.
    Prockop DJ, Fertala A (1998) J Struct Biol 122:111Google Scholar
  9. 9.
    Price RI, Lees S, Kirschner DA (1997) Int J Biol Macromol 20:23Google Scholar
  10. 10.
    Gutsmann T, Fantner GE, Venturoni M, Ekani-Nkodo A, Thompson JB, Kindt JH, Morse DE, Kuchnir Fygenson D, Hansma PK (2003) Biophys J 84:2593Google Scholar
  11. 11.
    Ottani V, Raspanti M, Ruggeri A (2001) Collagen structure and functional impications. Micron 32:251–260Google Scholar
  12. 12.
    Strlic M, Cigic IK, Rabin I, Kolar J, Pihlar B, Cassar M (2009) Autoxidation of lipids in parchment. Polym Degrad Stab 94(6):886–890Google Scholar
  13. 13.
    Larsen R, et al. (2005) Improved Damage Assessment of Parchment (IDAP), European project EVK4-CT-2001-00061. Available at: http://www.idap-parchment.dk.
  14. 14.
    Kennedy CJ, Hiller J, Odlyha M, Nielsen K, Drakopoulos M, Wess TJ (2002) Degradation in historical parchments: structural, biochemical and thermal studies. Pap Restaur 3(4):23–30Google Scholar
  15. 15.
    Della Gatta G, Badea E, Ceccarelli R, Usacheva T, Masic A, Coluccia S (2005) Assessment of damage in old parchments by DSC and SEM. J Therm Anal Calorim 82(3):637–649Google Scholar
  16. 16.
    Larsen R (ed) (2002) Microanalysis of parchment. European project SMT4-CT96-2106. Archetype Publications, CopenhagenGoogle Scholar
  17. 17.
    Kennedy CJ, Hiller JC, Lammie D, Drakopoulos M, Vest M, Cooper M, Adderley WP, Wess TJ (2004) Microfocus x-ray diffraction of historical parchment reveals variations in structural features through parchment cross sections. Nano Lett 4(8):1373–1380Google Scholar
  18. 18.
    Larsen R, Poulsen DV, Juchauld F, Jerosch H, Odlyha M, de Groot J, Wess T, Hiller J, Kennedy C, Della Gatta G, Badea E, Masic A, Boghosian S, Fessas D (2005) Damage assessment of parchment: complexity and relations at different structural levels. In: 14th ICOM-CC Meeting, Hague, pp 1–10Google Scholar
  19. 19.
    Giustetto R, Llabrès I, Xamena FX, Richiardi G, Bordiga F, Damin A, Gobetto R, Chierotti MR (2005) J Phys Chem B 109(41):19360–19368Google Scholar
  20. 20.
    Borgia GC, Camaiti M, Cerri F, Fantazzini P, Piacenti F (2003) Hydrophobic treatments for stone conservation: influence of application method on penetration, distribution and efficiency. Stud Conserv 48(4):217–226Google Scholar
  21. 21.
    Appolonia L, Borgia GC, Bortolotti V, Brown RJS, Fantazzini P, Rezzaro G (2001) Effects of hydrophobic treatments of stone on pore water studied by continuous distribution analysis of NMR relaxation times. Magn Reson Imaging 19:509–512Google Scholar
  22. 22.
    Casieri C, Bubici S, Viola I, De Luca F (2004) A low-resolution non-invasive NMR characterization of ancient paper. Solid State Nucl Magn Reson 26:65–73Google Scholar
  23. 23.
    Viola I, Bubici S, Casieri C, De Luca F (2004) The Codex Major of the Collectio Altaempsiana: a non-invasive NMR study of paper. J Cult Herit 5:257–261Google Scholar
  24. 24.
    Blümich B, Anferova S, Sharma S, Segre AL, Federici C (2003) Degradation of historical paper: nondestructive analysis by the NMR-MOUSE. J Magn Reson 161:204–209Google Scholar
  25. 25.
    Proietti N, Capitani D, Pedemonte E, Blumich B, Segre AL (2004) Monitoring degradation in paper: non-invasive analysis by unilateral NMR. Part II. J Magn Reson 170:113–120Google Scholar
  26. 26.
    Sharma S, Casanova F, Wache W, Segre A, Blumich B (2003) Analysis of historical porous building materials by the NMR-MOUSE. Magn Reson Imag 21:245–255Google Scholar
  27. 27.
    Proietti N, Capitani D, Lamanna R, Presciutti F, Rossi E, Segre AL (2005) Fresco paintings studied by unilateral NMR. J Magn Reson 177(1):111–117Google Scholar
  28. 28.
    Proietti N, Capitani D, Rossi E, Cozzolino S, Segre AL (2007) Unilateral NMR study of a XVI century wall painted. J Magn Reson 186(2):311–318Google Scholar
  29. 29.
    Capitani D, Emanuele MC, Segre A, Fanelli C, Fabbri AA, Attanasio D, Focher B, Capretti G (1998) Nord Pulp Pap Res J 13:95Google Scholar
  30. 30.
    Paci M, Federici C, Capitani D, Perenze N, Segre AL (1995) NMR study of paper. Carbohydr Polym 26(4):289–297Google Scholar
  31. 31.
    Capitani D, Emanuele MC, Bella J, Segre AL, Attanasio D, Focher B et al (1999) 1H NMR relaxation study of cellulose and water interaction in paper. Tappi J 82(9):117–124Google Scholar
  32. 32.
    Popescu C, Budrugeac P, Wortmann FJ, Miu L, Demco DE, Baias M (2008) Assessment of collagen-based materials which are supports of cultural and historical objects. Polym Degrad Stab 93(5):976–982Google Scholar
  33. 33.
    Badea E, Miu L, Budrugeac P, Giurginca M, Masic A, Badea N, Della Gatta G (2008) Study of deterioration of historical parchments by various thermal analysis techniques complemented by SEM, FTIR, UV-Vis-NIR and unilateral NMR investigations. J Therm Anal Calorim 91(1):17–27Google Scholar
  34. 34.
    Aliev AE (2005) Solid State NMR studies of collagen-based parchments and gelatin. Biopolymers 77:230–245Google Scholar
  35. 35.
    Rabin I, Brooke G, Hodgson J, Pantos M, Prag J (2007) The Ronald Reed archive at the John Rylands University Library. e-Preservation Science 4:9–12Google Scholar
  36. 36.
    Mogilner IG, Ruderman G, Raul Grigera J (2002) Collagen stability, hydration and native state. J Mol Graph Model 21:209–213Google Scholar
  37. 37.
    Luescher M, Ruegg MPS (1974) Effect of hydration upon the thermal stability of tropocollagen and its dependence on the presence of neutral salts. Biopolymers 13:2489–2503Google Scholar
  38. 38.
    Nomura S, Hiltner A, Lando JB, Baer E (1977) Interaction of water with native collagen. Biopolymers 16:231–246Google Scholar
  39. 39.
    Shinyashiki N, Asaka N, Mashimo S, Yagihara S, Hikichi K (1990) Microwave dielectric study on hydration of moist collagen. Biopolymers 29:1185–1191Google Scholar
  40. 40.
    Melacini G, Bonvin AMJJ, Goodman M, Boelens R, Kaptein R (2000) Hydration dinamics of the collagen triple helix by NMR. J Mol Biol 300:1041–1048Google Scholar
  41. 41.
    Kozlov PV, Burdygina GI (1983) The structure and properties of solid gelatin and the principles of their modification. Polymer 24:651–666Google Scholar
  42. 42.
    Fraser RDB, MacRae TP (1973) Conformation in fibrous proteins. Academic, New YorkGoogle Scholar
  43. 43.
    Bella J, Eaton M, Brodsky B, Berman H (1994) Science 266:75Google Scholar
  44. 44.
    Bella J, Brodsky B, Berman H (1995) Hydration structure of a collagen peptide. Structure 3:893–906Google Scholar
  45. 45.
    Pezron I, Djabourov M, Bosio L, Leblond J (1990) X-ray diffraction of gelatin fibres in the dry and swollen states. J Polym Sci part B-Polym Phys 28(10):1823–1839Google Scholar
  46. 46.
    Della Gatta G, Badea E, Masic A, Ceccarelli R (2007) Structural and Thermal Stability of Collagen within Parchment: a Mesoscopic and Molecular Approach. In: Larsen R (ed) Improved Damage Assessment of Parchment (IDAP) Collection and Sharing of Knowledge. Directorate-General for Research, Directorate Environment, European Communities, Brussels. pp 51–60Google Scholar
  47. 47.
    Della Gatta G, Badea E, Mašic A, Usacheva T, Benedetto S, Braghieri A Coparative study of environmental ageing-related changes in parchments by calorimetry and electron microscopy. In: ICOM-CC 14th Triennal Meeting, Hague, 12–16 September 2005. p 58Google Scholar
  48. 48.
    Ginell WS (1993) Report on Dead Sea Studies. The Getty Conservation Institute, Marina del Rey, CaliforniaGoogle Scholar
  49. 49.
    Ghioni C, Hiller JC, Kennedy CJ, Aliev AE, Odlyha M, Boulton M, Wess TJ (2005) Evidence of a distinct lipid fraction in historical parchments: a potential role in degradation? J Lipid Res 46(12):2726–2734Google Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • A. Masic
    • 1
    Email author
  • M. R. Chierotti
    • 2
  • R. Gobetto
    • 2
  • G. Martra
    • 2
  • I. Rabin
    • 3
  • S. Coluccia
    • 2
  1. 1.Department of BiomaterialsMax Planck Institute of Colloids and InterfacesPotsdamGermany
  2. 2.Department of Chemistry IFM and NIS Centre of ExcellenceUniversity of TorinoTorinoItaly
  3. 3.BAM Federal Institute for Materials Research and TestingBerlinGermany

Personalised recommendations