Abstract
It is well established that wood cellulose has highly ordered architecture at scales from a few nanometres to several microns in wood cell wall. Its preferred orientation could be in-situ investigated by polarized Raman spectroscopy. However, the technique is currently underused due to the challenges in sample preparation, instrumentation access and availability of prediction models. Here, a novel strategy is proposed to analyse the microfibril orientation without requiring prior knowledge of the fiber alignment. We derive the mathematical dependence between the incident light polarization angle and the intensity of Raman signal. An updated prediction model of microfibril orientation was thus constructed to replace the previous empirical functions. The problems of degradation and burning were addressed by adjusting the laser power and shortening the acquisition time. The orientation direction of cellulose microfibrils can be determined by the polarization-dependent 1096 cm−1 intensity without rotating sample. The strategy was successfully used to study the variations in molecular orientation throughout a cell wall of balsa wood. It was found that the cellulose microfibrils are arranged spirally to form the cell wall.
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The datasets generated during and/or analysed during the current study are not publicly available, but are available from the corresponding author or reasonable request.
References
Agarwal UP, Ralph SA (1997) FT-Raman spectroscopy of wood: identifying contributions of lignin and carbohydrate polymers in the spectrum of black spruce (Picea mariana). Appl Spectrosc 51(11):1648–1655. https://doi.org/10.1366/0003702971939316
Agarwal UP, Ralph SA, Reiner RS, Baez C (2016) Probing crystallinity of never-dried wood cellulose with Raman spectroscopy. Cellulose 23(1):125–144. https://doi.org/10.1007/s10570-015-0788-7
Agarwal UP, Ralph SA, Reiner RS, Baez C (2018) New cellulose crystallinity estimation method that differentiates between organized and crystalline phases. Carbohyd Polym 190:262–270. https://doi.org/10.1016/j.carbpol.2018.03.003
Atalla RH, Agarwal UP (1985) Raman microprobe evidence for lignin orientation in the cell walls of native woody tissue. Science 227(4687):636–638. https://doi.org/10.1126/science.227.4687.636
Barnett JR, Bonham VA (2004) Cellulose microfibril angle in the cell wall of wood fibres. Biol Rev 79(2):461–472. https://doi.org/10.1017/S1464793103006377
Côté WA, Day A, Timell T (1969) A contribution to the ultrastructure of tension wood fibers. Wood Sci Technol 3(4):257–271. https://doi.org/10.1007/BF00352301
Donaldson L (2008) Microfibril angle: measurement, variation and relationships–a review. Iawa J 29(4):345–386. https://doi.org/10.1163/22941932-90000192
Gierlinger N, Schwanninger M (2007) The potential of Raman microscopy and Raman imaging in plant research. Spectroscopy 21(2):69–89. https://doi.org/10.1155/2007/498206
Gierlinger N, Luss S, König C, Konnerth J, Eder M, Fratzl P (2010) Cellulose microfibril orientation of Picea abies and its variability at the micron-level determined by Raman imaging. J Exp Bot 61(2):587–595. https://doi.org/10.1093/jxb/erp325
Jorio A et al (2002) Polarized resonant Raman study of isolated single-wall carbon nanotubes: symmetry selection rules, dipolar and multipolar antenna effects. Phys Rev B 65(12):121402. https://doi.org/10.1103/physrevb.65.121402
Liu X-L, Zhang X, Lin M-L, Tan P-H (2017) Different angle-resolved polarization configurations of Raman spectroscopy: a case on the basal and edge plane of two-dimensional materials. Chin Phys B 26(6):067802. https://doi.org/10.1088/1674-1056/26/6/067802
Loudon R (2001) The Raman effect in crystals. AdvPhys 50(7):813–864. https://doi.org/10.1038/122477a0
Sun L et al (2016) Non-invasive imaging of cellulose microfibril orientation within plant cell walls by polarized Raman microspectroscopy. Biotechnol Bioeng 113(1):82–90. https://doi.org/10.1002/bit.25690
Svenningsson L, Lin Y-C, Karlsson M, Martinelli A, Nordstierna L (2019) Molecular orientation distribution of regenerated cellulose fibers investigated with polarized Raman spectroscopy. Macromolecules 52(10):3918–3924. https://doi.org/10.1021/acs.macromol.9b00520
Wiley JH, Atalla RH (1987) Band assignments in the Raman spectra of celluloses. Carbohyd Res 160:113–129. https://doi.org/10.1016/0008-6215(87)80306-3
Xue Y, Qiu X, Ouyang X (2020) Insights into the effect of aggregation on lignin fluorescence and its application for microstructure analysis. Int J Biol Macromol 154:981–988. https://doi.org/10.1016/j.ijbiomac.2020.03.056
Zhang X, Ji Z, Zhou X, Ma J-F, Hu Y-H, Xu F (2015) Method for automatically identifying spectra of different wood cell wall layers in Raman imaging data set. Anal Chem 87(2):1344–1350. https://doi.org/10.1021/ac504144s
Zhang X et al (2017) Method for removing spectral contaminants to improve analysis of Raman imaging data. Sci Rep 7(1):1–10. https://doi.org/10.1038/srep39891
Acknowledgements
The authors gratefully acknowledge the financial support from the Foundation of State Key Laboratory of Biobased Material and Green Papermaking (KF201902), the National Natural Science Foundation of China (32001272), and the Programme of Introducing Talents of Discipline to Universities (Project 111, B21022).
Funding
Foundation of State Key Laboratory of Biobased Material and Green Papermaking (KF201902). National Natural Science Foundation of China (32001272). Programme of Introducing Talents of Discipline to Universities (Project 111, B21022).
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Zhang, X., Li, L. & Xu, F. Polarized Raman spectroscopy for determining the orientation of cellulose microfibrils in wood cell wall. Cellulose 30, 75–85 (2023). https://doi.org/10.1007/s10570-022-04915-w
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DOI: https://doi.org/10.1007/s10570-022-04915-w