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Published in: Cellulose 17/2020

08-10-2020 | Original Research

Terahertz time-domain spectroscopy as a novel tool for crystallographic analysis in cellulose

Authors: Han Wang, Yoshiki Horikawa, Satoru Tsuchikawa, Tetsuya Inagaki

Published in: Cellulose | Issue 17/2020

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Abstract

Terahertz (THz) radiation is responsive to optical phonons in crystal lattices; therefore, THz time-domain spectroscopy (THz-TDS) has potential utility in crystallographic analysis. In this study, THz-TDS was used to investigate cellulose samples extracted from different sources with varying ratios of Iα and Iβ fractions. This is the first study to report that the absorption coefficient in the THz region of cellulose Iα and Iβ presents different characteristic absorption peaks around 2 THz. This can be used to distinguish the cellulose I allomorph, which exhibits differences in its crystalline structure. The absorption coefficient at 2.11 and 2.38 THz showed a considerable linear correlation with the Iα fraction of the cellulose samples. The absorption coefficient spectra of 1.88–3.40 THz were further detrended and separated into three Gaussian peaks. The correlations between the parameters of these separated peaks (integrated intensities, peak positions) and the crystalline structural values (d-spacing, crystalline size, crystallinity index) that calculated from the X-ray diffraction (XRD) pattern were investigated.

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Appendix
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Literature
go back to reference Agarwal UP, Ralph SA, Reiner RS, Baez C (2018) New cellulose crystallinity estimation method that differentiates between organized and crystalline phases. Carbohydr Polym 190:262–270CrossRef Agarwal UP, Ralph SA, Reiner RS, Baez C (2018) New cellulose crystallinity estimation method that differentiates between organized and crystalline phases. Carbohydr Polym 190:262–270CrossRef
go back to reference Atalla RH, VanderHart DL (1984) Native cellulose: a composite of two distinct crystalline forms. Science 223(4633):283–285CrossRef Atalla RH, VanderHart DL (1984) Native cellulose: a composite of two distinct crystalline forms. Science 223(4633):283–285CrossRef
go back to reference Azizi Samir MAS, Alloin F, Dufresne A (2005) Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite field. Biomacromol 6:612–626CrossRef Azizi Samir MAS, Alloin F, Dufresne A (2005) Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite field. Biomacromol 6:612–626CrossRef
go back to reference Belton PS, Tanner SF, Cartier N, Chanzy H (1989) High-resolution solid-state 13C nuclear magnetic resonance spectroscopy of tunicin, an animal cellulose. Macromolecules 22:1615–1617CrossRef Belton PS, Tanner SF, Cartier N, Chanzy H (1989) High-resolution solid-state 13C nuclear magnetic resonance spectroscopy of tunicin, an animal cellulose. Macromolecules 22:1615–1617CrossRef
go back to reference Blackwell J, Vasko PD, Koenig JL (1970) Infrared and raman spectra of the cellulose from the cellwall of valonia ventricosa. J Appl Phys 41:4375–4379CrossRef Blackwell J, Vasko PD, Koenig JL (1970) Infrared and raman spectra of the cellulose from the cellwall of valonia ventricosa. J Appl Phys 41:4375–4379CrossRef
go back to reference Debzi EM, Chanzy H, Sugiyama J et al (1991) The Iα → Iβ Transformation of Highly Crystalline Cellulose by Annealing in Various Mediums. Macromolecules 24:6816–6822CrossRef Debzi EM, Chanzy H, Sugiyama J et al (1991) The Iα → Iβ Transformation of Highly Crystalline Cellulose by Annealing in Various Mediums. Macromolecules 24:6816–6822CrossRef
go back to reference Federici JF, Schulkin B, Huang F et al (2005) THz imaging and sensing for security applications - Explosives, weapons and drugs. Semicond Sci Technol 2(7):S266–S230CrossRef Federici JF, Schulkin B, Huang F et al (2005) THz imaging and sensing for security applications - Explosives, weapons and drugs. Semicond Sci Technol 2(7):S266–S230CrossRef
go back to reference French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896CrossRef French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896CrossRef
go back to reference Horii F, Hirai A, Kitamaru R (1987a) CP/MAS13C NMR spectra of the crystalline components of native celluloses. Macromolecules 20:2117–2120CrossRef Horii F, Hirai A, Kitamaru R (1987a) CP/MAS13C NMR spectra of the crystalline components of native celluloses. Macromolecules 20:2117–2120CrossRef
go back to reference Horii F, Yamamoto H, Kitamaru R et al (1987b) Transformation of Native Cellulose Crystals Induced by Saturated Steam at High Temperatures. Macromolecules 20:2946–2949CrossRef Horii F, Yamamoto H, Kitamaru R et al (1987b) Transformation of Native Cellulose Crystals Induced by Saturated Steam at High Temperatures. Macromolecules 20:2946–2949CrossRef
go back to reference Horii F, Yamamoto H, Hirai A (1997) Microstructural Analysis of Microfibrils of Bacterial Cellulose. Macromol Symp 120:197–205CrossRef Horii F, Yamamoto H, Hirai A (1997) Microstructural Analysis of Microfibrils of Bacterial Cellulose. Macromol Symp 120:197–205CrossRef
go back to reference Horikawa Y (2017) Assessment of cellulose structural variety from different origins using near infrared spectroscopy. Cellulose 24:5313–5325CrossRef Horikawa Y (2017) Assessment of cellulose structural variety from different origins using near infrared spectroscopy. Cellulose 24:5313–5325CrossRef
go back to reference Horikawa Y, Sugiyama J (2009) Localization of crystalline allomorphs in cellulose microfibril. Biomacromol 10:2235–2239CrossRef Horikawa Y, Sugiyama J (2009) Localization of crystalline allomorphs in cellulose microfibril. Biomacromol 10:2235–2239CrossRef
go back to reference Ikeda Y, Ishihara Y, Moriwaki T et al (2010) A novel analytical method for pharmaceutical polymorphs by terahertz spectroscopy and the optimization of crystal form at the discovery stage. Chem Pharm Bull 58:76–81CrossRef Ikeda Y, Ishihara Y, Moriwaki T et al (2010) A novel analytical method for pharmaceutical polymorphs by terahertz spectroscopy and the optimization of crystal form at the discovery stage. Chem Pharm Bull 58:76–81CrossRef
go back to reference Imai T, Sugiyama J (1998) Nanodomains of Iα and Iβ cellulose in algal microfibrils. Macromolecules 31:6275–6279CrossRef Imai T, Sugiyama J (1998) Nanodomains of Iα and Iβ cellulose in algal microfibrils. Macromolecules 31:6275–6279CrossRef
go back to reference Imai T, Sugiyama J, Itoh T, Horii F (1999) Almost pure Iα cellulose in the cell wall of Glaucocystis. J Struct Biol 127:248–257CrossRef Imai T, Sugiyama J, Itoh T, Horii F (1999) Almost pure Iα cellulose in the cell wall of Glaucocystis. J Struct Biol 127:248–257CrossRef
go back to reference 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 Millim Terahertz Waves 35:949–961CrossRef 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 Millim Terahertz Waves 35:949–961CrossRef
go back to reference Larsson PT, Westermark U, Iversen T (1995) Determination of the cellulose Iα allomorph content in a tunicate cellulose by CP/MAS 13C-NMR spectroscopy. Carbohydr Res 278:339–343CrossRef Larsson PT, Westermark U, Iversen T (1995) Determination of the cellulose Iα allomorph content in a tunicate cellulose by CP/MAS 13C-NMR spectroscopy. Carbohydr Res 278:339–343CrossRef
go back to reference Makarem M, Lee CM, Kafle K et al (2019) Probing cellulose structures with vibrational spectroscopy. Cellulose 26:35–79CrossRef Makarem M, Lee CM, Kafle K et al (2019) Probing cellulose structures with vibrational spectroscopy. Cellulose 26:35–79CrossRef
go back to reference Marchessault RH, Pearson FG, Liang CY (1960) Infrared spectra of crystalline polysaccharides. Biochem Biophys Acta 45:499–507CrossRef Marchessault RH, Pearson FG, Liang CY (1960) Infrared spectra of crystalline polysaccharides. Biochem Biophys Acta 45:499–507CrossRef
go back to reference Nishiyama Y (2009) Structure and properties of the cellulose microfibril. J Wood Sci 55:241–249CrossRef Nishiyama Y (2009) Structure and properties of the cellulose microfibril. J Wood Sci 55:241–249CrossRef
go back to reference O’sullvian AC (1997) Cellulose: the structure slowly unravels. Cellulose 4:173–207CrossRef O’sullvian AC (1997) Cellulose: the structure slowly unravels. Cellulose 4:173–207CrossRef
go back to reference Park S, Baker JO, Himmel ME et al (2010) Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance. Biotechnol Biofuels 3:1–10CrossRef Park S, Baker JO, Himmel ME et al (2010) Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance. Biotechnol Biofuels 3:1–10CrossRef
go back to reference Peccianti M, Fastampa R, Mosca Conte A et al (2017) Terahertz absorption by cellulose: application to ancient paper artifacts. Phys Rev Appl 7:1–7CrossRef Peccianti M, Fastampa R, Mosca Conte A et al (2017) Terahertz absorption by cellulose: application to ancient paper artifacts. Phys Rev Appl 7:1–7CrossRef
go back to reference Persson J, Chanzy H, Sugiyama J (1991) Combined infrared and electron diffraction study of the polymorphism of native celluloses. Macromolecules 24:2461–2466CrossRef Persson J, Chanzy H, Sugiyama J (1991) Combined infrared and electron diffraction study of the polymorphism of native celluloses. Macromolecules 24:2461–2466CrossRef
go back to reference Reid M, Fedosejevs R (2006) Terahertz birefringence and attenuation properties of wood and paper. Appl Opt 45:2766–2772CrossRef Reid M, Fedosejevs R (2006) Terahertz birefringence and attenuation properties of wood and paper. Appl Opt 45:2766–2772CrossRef
go back to reference Strachan CJ, Taday PF, Newnham DA et al (2005) Using terahertz pulsed spectroscopy to quantify pharmaceutical polymorphism and crystallinity. J Pharm Sci 94:837–846CrossRef Strachan CJ, Taday PF, Newnham DA et al (2005) Using terahertz pulsed spectroscopy to quantify pharmaceutical polymorphism and crystallinity. J Pharm Sci 94:837–846CrossRef
go back to reference Sugiyama J, Vuong R, Chanzy H (1991) Electron diffraction study on the two crystalline phases occurring in native cellulose from an algal cell wall. Macromolecules 24:4168–4175CrossRef Sugiyama J, Vuong R, Chanzy H (1991) Electron diffraction study on the two crystalline phases occurring in native cellulose from an algal cell wall. Macromolecules 24:4168–4175CrossRef
go back to reference Taday PF, Bradley IV, Arnone DD, Pepper M (2003) Using terahertz pulse spectroscopy to study the crystalline structure of a drug: a case study of the polymorphs of ranitidine hydrochloride. J Pharm Sci 92:831–838CrossRef Taday PF, Bradley IV, Arnone DD, Pepper M (2003) Using terahertz pulse spectroscopy to study the crystalline structure of a drug: a case study of the polymorphs of ranitidine hydrochloride. J Pharm Sci 92:831–838CrossRef
go back to reference Takahashi M (2014) Terahertz vibrations and hydrogen-bonded networks in crystals. Crystals 4:74–103CrossRef Takahashi M (2014) Terahertz vibrations and hydrogen-bonded networks in crystals. Crystals 4:74–103CrossRef
go back to reference Updegraff DM (1969) Semimicro determination of cellulose inbiological materials. Anal Biochem 32:420–424CrossRef Updegraff DM (1969) Semimicro determination of cellulose inbiological materials. Anal Biochem 32:420–424CrossRef
go back to reference VanderHart DL, Atalla RH (1984) Studies of microstructure in native celluloses using solid-state 13C NMR. Macromolecules 17:1465–1472CrossRef VanderHart DL, Atalla RH (1984) Studies of microstructure in native celluloses using solid-state 13C NMR. Macromolecules 17:1465–1472CrossRef
go back to reference Vieira FS, Pasquini C (2014) Determination of cellulose crystallinity by terahertz-time domain spectroscopy. Anal Chem 86:3780–3786CrossRef Vieira FS, Pasquini C (2014) Determination of cellulose crystallinity by terahertz-time domain spectroscopy. Anal Chem 86:3780–3786CrossRef
go back to reference Wada M, Okano T (2001) Localization of Iα and Iβ phases in algal cellulose revealed by acid treatments. Cellulose 8:183–188CrossRef Wada M, Okano T (2001) Localization of Iα and Iβ phases in algal cellulose revealed by acid treatments. Cellulose 8:183–188CrossRef
go back to reference Wada M, Sugiyama J, Okano T (1993) Native celluloses on the basis of two crystalline phase (Iα/Iβ) system. J Appl Polym Sci 49:1491–1496CrossRef Wada M, Sugiyama J, Okano T (1993) Native celluloses on the basis of two crystalline phase (Iα/Iβ) system. J Appl Polym Sci 49:1491–1496CrossRef
go back to reference Wada M, Okano T, Sugiyama J (1997) Synchrotron-radiated X-ray and neutron diffraction study of native cellulose. Cellulose 4:221–232CrossRef Wada M, Okano T, Sugiyama J (1997) Synchrotron-radiated X-ray and neutron diffraction study of native cellulose. Cellulose 4:221–232CrossRef
go back to reference Wada M, Okano T, Sugiyama J (2001) Allomorphs of native crystalline cellulose I evaluated by two equatorial d-spacings. J Wood Sci 47:124–128CrossRef Wada M, Okano T, Sugiyama J (2001) Allomorphs of native crystalline cellulose I evaluated by two equatorial d-spacings. J Wood Sci 47:124–128CrossRef
go back to reference 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 Millim Terahertz Waves 40:673–687CrossRef 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 Millim Terahertz Waves 40:673–687CrossRef
go back to reference Yamamoto H, Horii F (1993) CP/MAS 13C NMR analysis of the crystal transformation induced for valonia cellulose by annealing at high temperatures. Macromolecules 26:1313–1317CrossRef Yamamoto H, Horii F (1993) CP/MAS 13C NMR analysis of the crystal transformation induced for valonia cellulose by annealing at high temperatures. Macromolecules 26:1313–1317CrossRef
go back to reference Zsigmondy R, Scherrer P (1912) Bestimmung der inneren Struktur und der Größe von Kolloidteilchen mittels Röntgenstrahlen. Kolloidchem Ein Lehrb 277:387–409 Zsigmondy R, Scherrer P (1912) Bestimmung der inneren Struktur und der Größe von Kolloidteilchen mittels Röntgenstrahlen. Kolloidchem Ein Lehrb 277:387–409
Metadata
Title
Terahertz time-domain spectroscopy as a novel tool for crystallographic analysis in cellulose
Authors
Han Wang
Yoshiki Horikawa
Satoru Tsuchikawa
Tetsuya Inagaki
Publication date
08-10-2020
Publisher
Springer Netherlands
Published in
Cellulose / Issue 17/2020
Print ISSN: 0969-0239
Electronic ISSN: 1572-882X
DOI
https://doi.org/10.1007/s10570-020-03508-9

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