Abstract
In the framework of a study on the aging phenomena of textiles we used Raman spectral mapping to analyze changes in the chemical bonds of cellulose of flax fabrics exposed to ultraviolet (UV) radiation in air, and extreme ultraviolet (EUV) radiation in vacuum. Our results show that both UV and EUV produce photolysis of cellulose bonds, which in turn triggers photochemical oxidation and dehydration, in a kind of “accelerated aging” and oxidative degradation of flax. In particular, we detected the formation of a large number of carboxyl and carbonyl groups, which, when conjugated, act as chromophores and give flax a yellowish hue. Remarkably, the mapping of Raman spectra makes it possible to identify the relative weights of molecular reactions responsible for the generation of oxidized groups and aging of cellulose. In particular, the comparison of spatially-resolved Raman spectra after irradiations UV in air and EUV in vacuum provides direct and quantitative evidence of the role of oxygen in the molecular changes leading to flax aging due to UV illumination. As an example, we found that atmospheric oxygen does not affect the change of the degree of polymerization of cellulose nor the formation of carboxyl and carboxyl groups. These results help to assess the possible benefit, if any, of preserving and exposing ancient cellulosic cloths in an inert, oxygen-free atmosphere.
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References
Agarwal UP, Reiner RS, Ralph SA (2010) Cellulose I crystallinity determination using FT–Raman spectroscopy: univariate and multivariate methods. Cellulose 17:721. https://doi.org/10.1007/s10570-010-9420-z
Balakhnina IA, Brandt NN, Chikishev AY, Rebrikova NL (2018) Raman microspectroscopy of old paper samples with foxing. Appl Spectrosc 68:495. https://doi.org/10.1366/13-07222
Bollanti S, Di Lazzaro P, Flora F, Mezi L, Murra D, Torre A (2015) Space- and time-resolved diagnostics of the ENEA EUV discharge-produced-plasma source used for metrology and other applications. High Power Laser Sci Eng 3:e29–e26. https://doi.org/10.1017/hpl.2015.30
Botti S, Bonfigli F, Nigro V, Rufoloni A, Vannozzi A (2022) Evaluating the conservation state of naturally aged paper with Raman and luminescence spectral mapping: toward a non-destructive diagnostic protocol. Molecules 27:1712. https://doi.org/10.3390/molecules27051712
Chiriu D, Ricci PC, Cappellini G, Salis M, Loddo G, Carbonaro CM (2018) Ageing of ancient paper: a kinetic model of cellulose degradation from Raman spectra. J Raman Spectrosc 49:1802. https://doi.org/10.1002/jrs.5462
Cuttle C, Feibse M, Iesna F (1996) Damage to museum objects due to light exposure. Light Res Technol 28:1–9. https://doi.org/10.1177/14771535960280010301
Di Lazzaro P, Murra D (2015) Shroud like coloration of linen, conservation measures and perception of patterns onto the Shroud of Turin. SHS Web Confe 15:00005. https://doi.org/10.1051/shsconf/20151500005
Di Lazzaro P, Murra D, Nichelatti E, Santoni A, Baldacchini G (2012) Superficial and shroud-like coloration of linen by short laser pulses in the vacuum ultraviolet. Appl Opt 51:8567–8578. https://doi.org/10.1364/AO.51.008567
Gilbert R, Gilbert MM (1980) Ultraviolet-visible reflectance and fluorescence spectra of the shroud of Turin. Appl Opt 19:1930–1936. https://doi.org/10.1364/AO.19.001930
Heitner C (1993) Light: induced yellowing of wood containing papers. Chapter 1 in Photochemistry of lignocellulosic materials, ACS symposium series, American Chemical Society, Washington DC
Heller JH, Adler AD (1981) A chemical investigation of the shroud of Turin. Can Soc Forensic Sci J 14:81–103. https://doi.org/10.1080/00085030.1981.10756882
Henke BL, Gullikson EM, Davis JC (1993) X-ray interactions: photoabsorption, scattering, transmission and reflection at E = 50 – 30.000 eV, Z = 1–92. At Data Nucl Data Tables 54:181–342
Iacomussi P, Radis M, Valpreda F, Rossi G, Di Lazzaro P (2018) Lighting the Shroud of Turin for exhibition in 2015. Stud Conserv 63:S127–S131. https://doi.org/10.1080/00393630.2018.1504442
Jumper EJ, Adler AD, Jackson JP, Pellicori SF, Heller JH, Druzik JR (1984) A comprehensive examination of the various stains and images on the shroud of Turin. Archaeological chemistry III: ACS advances in chemistry 205. American Chemical Society, Washington, pp 447–476
Kolar J, Dtrlic M, Pentzien S, Kautek W (2000) Near UV, visible and IR pulsed laser light interaction with cellulose. Appl Phys A 71:87–90. https://doi.org/10.1007/PL00021097
Korntner P, Hosoya T, Dietz T et al (2015) Chromophores in lignin-free cellulosic materials belong to three compound classes. Chromophores in cellulosics, XII. Cellulose 22:1053–1062. https://doi.org/10.1007/s10570-015-0566-6
Lewis IR, Howell Edwards GM (2021) Handbook of Raman spectroscopy, from the research laboratory to the process line. CRC Press Inc. ISBN 10 1439868077
Malešič J, Kolar J, Strlič M, Kočar D, Fromageot D, Lemaire J, Haillant O (2005) Photo-induced degradation of cellulose. Polym Degrad Stab 89:64–69. https://doi.org/10.1016/j.polymdegradstab.2005.01.003
Merlin A, Fouassier J (1980) Photochemical investigations into cellulosic materials I. Free radical generation in cellulose by photosensitized excitation. Die Angewandte Makromolekulare Chemie 86:109–121. https://doi.org/10.1002/apmc.1980.050860108
Mezi L (2022) Characterization of the ENEA extreme ultraviolet radiation discharge produced plasma source, by using diamond detectors developed at the University of Rome Tor Vergata. Il Nuovo Cimento 45C:88. https://www.sif.it/riviste/sif/ncc/econtents/2022/045/04/article/23
Mezi L, Bollanti S, Botti S, Brusatin G, Businaro L, Della Giustina G, Di Lazzaro P, Fagnoni M, Flora F, Gerardino A, Murra D, Protti S, Torre A, Torti E The ENEA discharge produced plasma extreme ultraviolet source and its patterning applications. Proc. SPIE vol. 11042 (SPIE, Bellingham WA (2019) 2019), pp. 110420Z-1/110420Z-6. https://doi.org/10.1117/12.2522469
Mosca Conte A, Pulci O, Knapik A, Bagniuk J, Del Sole R, Łojewska J, Missori M (2012) Role of cellulose oxidation in the yellowing of ancient paper. Phys Rev Lett 108:158301–158305. https://doi.org/10.1103/PhysRevLett.108.158301
Niyazi F, Savenkova IV, Zaikov GE (2005) Photodegradation and light stabilization of heterochain polymers. Book News, Inc, Portland
Phillips GO, Arthur JC Jr (1985) Photochemistry and radiation chemistry of cellulose. Zeronian S.H. Editor. Ellis Horwood Ltd, UK
Potthast A, Rosenau T, Kosma P et al (2005) On the nature of carbonyl groups in cellulosic pulps. Cellulose 12:43–50. https://doi.org/10.1023/B:CELL.0000049347.01147.3d
Potthast A, Schiehser S, Rosenau T, Sixta H, Kosma P (2004) Effect of UV radiation on the carbonyl distribution in different pulps. Holzforschung 58:597–602. https://doi.org/10.1515/hf.2004.113
Proniewicz M, Paluszkiewicz C, Wesełucha-Birczyńska A, Majcherczyk H, Barański A, Konieczna A (2001) FT-IR and FT-Raman study of hydrothermally degraded cellulose. J Mol Struct 596:163–169. https://doi.org/10.1016/S0022-2860(01)00706-2
Rosenau T, Potthast A, Kosma P, Suess H, Nimmerfroh N (2007) Isolation and identification of residual chromophores from aged bleached pulp samples. Cellulose 61:656–661. https://doi.org/10.1515/HF.2007.108
Rosenau T, Potthast A, Krainz K, Yoneda Y, Dietz T, Peralta-Inga Shields Z, French AD (2011) Chromophores in cellulosics, VI. First isolation and identification of residual chromophores from aged cotton linters. Cellulose 18:1623–1633. https://doi.org/10.1007/s10570-011-9585-0
Thiéry JP (1967) Mise en évidence des polysaccharides sur coupes fines en microscopie électronique. J De Microscopie et de Biol cellulaire 6:927–1017
UNIEN (2014) CEN/TS 16163 conservation of cultural heritage-guidelines and procedures for choosing appropriate lighting for indoor exhibitions. https://standards.iteh.ai/catalog/standards/cen/eb0885a3-d2d9-4eb8-bd43-da7b58f8b237/cen-ts-16163-2014
Vosmanská V, Barb RA, Kolářová K, Rimpelová S, Heitz J (2016) Effect of VUV-excimer lamp treatment on cellulose fiber. Int J Polym Anal Charact 21:337–347. https://doi.org/10.1080/1023666X.2016.1156897
Wiley JH, Atalla RH (1987) Band assignments in the Raman spectra of celluloses. Carbohydr Res 160:113–129. https://doi.org/10.1016/0008-6215(87)80306-3
Yan L, Chouw N, Jayaraman K (2014) Flax fibre and its composites-a review. Compos Part B Eng 56:296–317. https://doi.org/10.1016/j.compositesb.2013.08.014
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Botti, S., Di Lazzaro, P., Flora, F. et al. Raman spectral mapping reveal molecular changes in cellulose aging induced by ultraviolet and extreme ultraviolet radiation. Cellulose 31, 749–758 (2024). https://doi.org/10.1007/s10570-023-05681-z
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DOI: https://doi.org/10.1007/s10570-023-05681-z