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Terahertz time-domain spectroscopy as a novel tool for crystallographic analysis in cellulose: cellulose I to cellulose II, tracing the structural changes under chemical treatment

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Abstract

Terahertz time-domain spectroscopy (THz-TDS) has expanded possibilities in cellulose crystallography research, as THz radiation detects most intermolecular vibrations and responds to the phonons of crystalline lattices. In this study, we traced the transformation of the cellulose crystalline lattice from cellulose I to cellulose II by THz-TDS and X-ray powder diffraction. Cellulose II was obtained by treating cellulose I with NaOH of different concentrations (0 wt%–20 wt%, at 2 wt% intervals). The THz absorption coefficient spectra of cellulose II showed three characteristic peaks (at 1.32 THz, 1.76 THz, and 2.77 THz). The THz absorption coefficient spectra of cellulose II treated with 20-wt% NaOH and cellulose I without NaOH treatment were fitted by a seventh-order Fourier series. Thus, the THz absorption coefficient spectra of samples treated with NaOH of other concentrations could be considered a combination of these two fitted profiles of cellulose I and cellulose II, multiplied by different coefficients. Furthermore, the coefficients could reflect the relative contents of cellulose I and cellulose II in the samples.

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References

  • Arora A, Luong TQ, Krüger M et al (2012) Terahertz-time domain spectroscopy for the detection of PCR amplified DNA in aqueous solution. Analyst 137:575–579

    Article  CAS  Google Scholar 

  • Bragg WH, Bragg WL (1913) The reflection of X-rays by crystals. Proc R Soc London Ser A Contain Pap Math Phys Character 88:428–438

    CAS  Google Scholar 

  • Brown RM (2004) Cellulose structure and biosynthesis: what is in store for the 21st century? J Polym Sci A Polym Chem 42:487–495

    Article  CAS  Google Scholar 

  • Ebbinghaus S, Seung JK, Heyden M et al (2007) An extended dynamical hydration shell around proteins. Proc Natl Acad Sci USA 104:20749–20752

    Article  CAS  Google Scholar 

  • El-Oudiani A, Chaabouni Y, Msahli S, Sakli F (2011) Crystal transition from cellulose i to cellulose II in NaOH treated Agave americana L. fibre. Carbohydr Polym 86:1221–1229

    Article  CAS  Google Scholar 

  • Fellers RS, Leforestier C, Braly LB et al (1999) Spectroscopic determination of the water pair potential. Science 284:945–948

    Article  CAS  Google Scholar 

  • Halonen H, Larsson PT, Iversen T (2013) Mercerized cellulose biocomposites: a study of influence of mercerization on cellulose supramolecular structure, water retention value and tensile properties. Cellulose 20:57–65

    Article  CAS  Google Scholar 

  • Hermans PH, Weidinger A (1946) On the recrystallization of amorphous cellulose. J Am Chem Soc 68:2547–2552

    Article  CAS  Google Scholar 

  • Inagaki T, Ahmed B, Hartley ID et al (2014) Simultaneous prediction of density and moisture content of wood by terahertz time domain spectroscopy. J Infrared Millimeter Terahertz Waves 35:949–961

    Article  Google Scholar 

  • Kafle K, Greeson K, Lee C, Kim SH (2014) Cellulose polymorphs and physical properties of cotton fabrics processed with commercial textile mills for mercerization and liquid ammonia treatments. Text Res J 84:1692–1699

    Article  Google Scholar 

  • Kolpak FJ, Blackwell J (1976) Determination of the structure of cellulose II. Macromolecules 9:273–278

    Article  CAS  Google Scholar 

  • Langan P, Nishiyama Y, Chanzy H (1999) A revised structure and hydrogen-bonding system in cellulose II from a neutron fiber diffraction analysis. J Am Chem Soc 121:9940–9946

    Article  CAS  Google Scholar 

  • Langan P, Nishiyama Y, Chanzy H (2001) X-ray structure of mercerized cellulose II at 1 Å resolution. Biomacromol 2:410–416

    Article  CAS  Google Scholar 

  • Markelz AG (2008) Terahertz dielectric sensitivity to biomolecular structure and function. IEEE J Sel Top Quantum Electron 14:180–190

    Article  CAS  Google Scholar 

  • Markelz AG, Roitberg A, Heilweil EJ (2000) Pulsed terahertz spectroscopy of DNA, bovine serum albumin and collagen between 0.1 and 2.0 THz. Chem Phys Lett 320:42–48

    Article  CAS  Google Scholar 

  • O’sullvian AC (1997) Cellulose: the structure slowly unravels. Cellulose 4:173–207

    Article  Google Scholar 

  • Oh SY, Dong IY, Shin Y et al (2005) Crystalline structure analysis of cellulose treated with sodium hydroxide and carbon dioxide by means of X-ray diffraction and FTIR spectroscopy. Carbohydr Res 340:2376–2391

    Article  CAS  Google Scholar 

  • Peccianti M, Fastampa R, Mosca Conte A et al (2017) Terahertz absorption by cellulose: application to ancient paper artifacts. Phys Rev Appl 7:064019

    Article  Google Scholar 

  • Reid M, Fedosejevs R (2006) Terahertz birefringence and attenuation properties of wood and paper. Appl Opt 45:2766–2772

    Article  Google Scholar 

  • Schenzel K, Fischer S (2001) NIR FT Raman spectroscopy: a rapid analytical tool for detecting the transformation of cellulose polymorphs. Cellulose 8:49–57

    Article  CAS  Google Scholar 

  • Schenzel K, Almlöf H, Germgård U (2009) Quantitative analysis of the transformation process of cellulose I → cellulose II using NIR FT Raman spectroscopy and chemometric methods. Cellulose 16:407–415

    Article  CAS  Google Scholar 

  • Shiraga K, Ogawa Y, Kondo N (2016) Hydrogen bond network of water around protein investigated with terahertz and infrared spectroscopy. Biophys J 111:2629–2641

    Article  CAS  Google Scholar 

  • Strachan CJ, Taday PF, Newnham DA et al (2005) Using terahertz pulsed spectroscopy to quantify pharmaceutical polymorphism and crystallinity. J Pharm Sci 94:837–846

    Article  CAS  Google Scholar 

  • Todoruk TM, Hartley ID, Reid ME (2012) Origin of birefringence in wood at terahertz frequencies. IEEE Trans Terahertz Sci Technol 2:123–130

    Article  Google Scholar 

  • Vieira FS, Pasquini C (2014) Determination of cellulose crystallinity by terahertz-time domain spectroscopy. Anal Chem 86:3780–3786

    Article  CAS  Google Scholar 

  • Wang H, Inagaki T, Hartley ID et al (2019) Determination of dielectric function of water in THz region in wood cell wall result in an accurate prediction of moisture content. J Infrared Millimeter Terahertz Waves 40:673–687

    Article  CAS  Google Scholar 

  • Wang H, Horikawa Y, Tsuchikawa S, Inagaki T (2020) Terahertz time-domain spectroscopy as a novel tool for crystallographic analysis in cellulose. Cellulose 27:9767–9777

    Article  CAS  Google Scholar 

  • Wang H, Tsuchikawa S, Inagaki T (2021) Terahertz time-domain spectroscopy as a novel tool for crystallographic analysis in cellulose: the potentiality of being a new standard for evaluating crystallinity. Cellulose 28:5293–5304

    Article  CAS  Google Scholar 

  • Yada H, Nagai M, Tanaka K (2009) The intermolecular stretching vibration mode in water isotopes investigated with broadband terahertz time-domain spectroscopy. Chem Phys Lett 473:279–283

    Article  CAS  Google Scholar 

  • Zeitler JA, Kogermann K, Rantanen J et al (2007) Drug hydrate systems and dehydration processes studied by terahertz pulsed spectroscopy. Int J Pharm 334:78–84

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by JSPS KAKENHI Grant Number 21H02255 and 16H02559. The XRD measurement was supported by Radioisotope Research Center, Nagoya University. And the first author also thanks for the Mitsutani scholarship for living support.

Funding

JSPS KAKENHI Grant Number 21H02255 and 16H02559.

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Authors and Affiliations

  1. Graduate School of Bioagricultural Sciences, Nagoya University, Nagoya, Aichi, 464-8601, Japan

    Han Wang, Hiroki Kataoka, Satoru Tsuchikawa & Tetsuya Inagaki

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  1. Han Wang
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  2. Hiroki Kataoka
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  3. Satoru Tsuchikawa
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  4. Tetsuya Inagaki
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Contributions

Han Wang and Tetsuya Inagaki conceived and designed the experiments. Han Wang and Hiroki Kataoka performed the experiments and analyzed the data. Han Wang wrote the paper, Tetsuya Inagaki and Satoru Tsuchikawa gave final approval of the manuscript.

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Correspondence to Tetsuya Inagaki.

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This study following Compliance with Ethical Standards; this study does not involve human participants, animals, and potential conflicts of interest.

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Wang, H., Kataoka, H., Tsuchikawa, S. et al. Terahertz time-domain spectroscopy as a novel tool for crystallographic analysis in cellulose: cellulose I to cellulose II, tracing the structural changes under chemical treatment. Cellulose 29, 3143–3151 (2022). https://doi.org/10.1007/s10570-022-04493-x

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