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Elucidation of alcoholysis for the preparation of lignin-free wood sections from Cryptomeria japonica

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Abstract

This study reports on the preparation of lignin-free wood sections maintaining the anatomical structure of Cryptomeria japonica by means of alcoholysis combined with sodium chlorite treatment. To determine the optimal alcoholysis conditions, Fourier transform infrared spectroscopy was combined with multivariate analysis, and the obtained results indicated that the alcoholysis reaction proceeded over three stages. In the first stage, lignin and hemicellulose are partially removed. In the second stage, hemicellulose and amorphous cellulose are degraded and humin is formed. In the third stage, crystalline cellulose is degraded, further promoting the formation of humin. Since it is difficult to completely remove lignin by alcoholysis alone, the wood sections were subsequently subjected to sodium chlorite treatment. As a result, lignin-free sections were produced without degradation of the woody anatomical structure. Furthermore, alcoholysis at 140 °C for 1 h coupled with sodium chlorite treatment for 1 h succeeded in producing sections composed of essentially hemicellulose-free cellulose. These achievements make this protocol potentially applicable as a substrate for artificial cell walls and for the development of novel functional filters.

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References

  • Abe H, Ohtani J, Fukazawa K (1991) Microfibrillar orientation in tracheid walls. IAWA Bull 12:431–438

    Google Scholar 

  • Åkerholm M, Salmén L (2001) Interactions between wood polymers studied by dynamic FT-IR spectroscopy. Polymer 42:963–969

    Google Scholar 

  • Barakat A, Winter H, Rondeau-Mouro C, Saake B, Chabbert B, Cathala B (2007) Studies of xylan interactions and cross-linking to synthetic lignins formed by bulk and end-wise polymerization: a model study of lignin carbohydrate complex formation. Planta 226:267–281

    CAS  PubMed  Google Scholar 

  • Berglund J, Mikkelsen D, Flanagan BM, Dhital S, Gaunitz S, Henriksson G, Lindström ME, Yakubov GE, Gidley MJ, Vilaplana F (2020) Wood hemicelluloses exert distinct biomechanical contributions to cellulose fibrillar networks. Nat Commun 11:4692

    CAS  PubMed  PubMed Central  Google Scholar 

  • Busse-Wicher M, Gomes TCF, Tryfona T, Nikolovski N, Stott K, Grantham NJ, Bolam DN, Skaf MS, Dupree P (2014) The pattern of xylan acetylation suggests xylan may interact with cellulose microfibrils as a twofold helical screw in the secondary plant cell wall of Arabidopsis thaliana. Plant J 79:492–506

    CAS  PubMed  PubMed Central  Google Scholar 

  • Busse-Wicher M, Li A, Silveira RL, Pereira CS, Tryfona T, Gomes TCF, Skaf MS, Dupree P (2016) Evolution of xylan substitution patterns in gymnosperms and angiosperms: implications for xylan interaction with cellulose. Plant Physiol 171:2418–2431

    CAS  PubMed  PubMed Central  Google Scholar 

  • Derkacheva O, Sukhov D (2008) Investigation of lignins by FTIR spectroscopy. Macromol Symp 265:61–68

    CAS  Google Scholar 

  • Du B, Chai L, Li W, Wang X, Chen X, Zhou J (2022) Preparation of functionalized magnetic graphene oxide/lignin composite nanoparticles for adsorption of heavy metal ions and reuse as electromagnetic wave absorbers. Sep Purif Technol 297:121509

    CAS  Google Scholar 

  • Faix O (1991) Classification of lignins from different botanical origins by FT-IR spectroscopy. Holzforschung 45:21–28

    CAS  Google Scholar 

  • Fengel D, Wegener G (1989) Wood: chemistry, ultrastructure, reactions. Walter de Gruyter, Berlin

    Google Scholar 

  • Freudenberg K, Neish AC (1968) Constitution and biosynthesis of lignin. Springer, Berlin

    Google Scholar 

  • Fu Q, Ansari F, Zhou Q, Berglund LA (2018) Wood nanotechnology for strong, mesoporous, and hydrophobic biocomposites for selective separation of oil/water mixtures. ACS Nano 12:2222–2230

    CAS  PubMed  Google Scholar 

  • Fukushima K, Terashima N (1991) Heterogeneity in formation of lignin. 14. Formation and structure of lignin in differentiating xylem of Ginkgo biloba. Holzforschung 45:87–94

    CAS  Google Scholar 

  • Hage RE, Brosse N, Sannigrahi P, Ragauskas A (2010) Effects of process severity on the chemical structure of Miscanthus ethanol organosolv lignin. Polym Deg Stab 95:997–1003

    Google Scholar 

  • Hallac BB, Ray M, Murphy RJ, Ragauskas AJ (2011) Review analyzing cellulose degree of polymerization and its relevancy to cellulosic ethanol. Biotechnol Bioeng 107:795–801

    Google Scholar 

  • Hernández M, Hernández-Coronado MJ, Pérez MI, Revilla E, Villar JC, Ball AS, Viikari L, Arias ME (2005) Biomechanical pulping of spruce wood chips with Streptomyces cyaneus CECT 3335 and handsheet characterization. Holzforschung 59:173

    Google Scholar 

  • Higuchi T, Ogino K, Tanahashi M (1971) Effect of polysaccharides on dehydropolymerization of coniferyl alcohol. Wood Res 51:1–11

    Google Scholar 

  • Hirano S, Yamagishi Y, Nakaba S, Kajita S, Funada R, Horikawa Y (2020) Artificial lignified cell wall catalyzed by peroxidase selectively localized on a network of microfibrils from cultured cells. Planta 251:104

    CAS  PubMed  Google Scholar 

  • Horikawa Y, Imai T, Takada R, Watanabe T, Takabe K, Kobayashi Y, Sugiyama J (2011) Near-infrared chemometric approach to exhaustive analysis of rice straw pretreated for bioethanol conversion. Appl Biochem Biotechnol 164:194–203

    CAS  PubMed  Google Scholar 

  • Horikawa Y, Hirano S, Mihashi A, Kobayashi Y, Zhai S, Sugiyama J (2019) Prediction of lignin contents from infrared spectroscopy: chemical digestion and lignin/biomass ratios of Cryptomeria japonica. Appl Biochem Biotechnol 188:1066–1076

    CAS  PubMed  Google Scholar 

  • Horikawa Y, Tsushima R, Noguchi K, Nakaba S, Funada R (2020) Development of colorless wood via two-step delignification involving alcoholysis and bleaching with maintaining natural hierarchical structure. J Wood Sci 66:37

    CAS  Google Scholar 

  • Hu X, Lievens C, Larcher A, Li CZ (2011) Reaction pathways of glucose during esterification: effects of reaction parameters on the formation of humin type polymers. Bioresour Technol 102:10104–10113

    CAS  PubMed  Google Scholar 

  • Kataoka Y, Saiki H, Fujita M (1992) Arrangement and superposition of cellulose microfibrils in the secondary walls of coniferous tracheids. Mokuzai Gakkaishi 38:327–355

    CAS  Google Scholar 

  • Kim JS, Awano T, Yoshinaga A, Takabe K (2010a) Temporal and spatial immunolocalization of glucomannans in differentiating earlywood tracheid cell walls of Cryptomeria japonica. Planta 232:545–554

    CAS  PubMed  Google Scholar 

  • Kim JS, Awano T, Yoshinaga A, Takabe K (2010b) Immunolocalization and structural variations of xylan in differentiating earlywood tracheid cell walls of Cryptomeria japonica. Planta 232:817–824

    CAS  PubMed  Google Scholar 

  • Kiyoto SA, Yoshinaga A, Takabe K (2015) Relative deposition of xylan and 8-5-linked lignin structure in Chamaecyparis obtusa, as revealed by double immunolabeling by using monoclonal antibodies. Planta 241:243–256

    CAS  PubMed  Google Scholar 

  • Kurei T, Tsushima R, Okahisa Y, Nakaba S, Funada R, Horikawa Y (2021) Creation and structural evaluation of the three-dimensional cellulosic material “White-Colored Bamboo.” Holzforschung 75(2):180–186

    CAS  Google Scholar 

  • Li Q, Koda K, Yoshinaga A, Takabe K, Shimomura M, Hirai Y, Tamai Y, Uraki Y (2015) Dehydrogenative polymerization of coniferyl alcohol in artificial polysaccharides matrices: effects of xylan on the polymerization. J Agric Food Chem 63:4613–4620

    CAS  PubMed  Google Scholar 

  • Lyu Y, Matsumoto T, Taira S, Ijiri K, Yoshinaga A, Shigetomi K, Uraki Y (2021) Influences of polysaccharides in wood cell walls on lignification in vitro. Cellulose 28:9907–9917

    CAS  Google Scholar 

  • Maeda Y, Awano T, Takabe K, Fujita M (2000) Immunolocalization of glucomannans in the cell wall of differentiating tracheids in Chamaecyparis obtuse. Protoplasma 213:148–156

    CAS  Google Scholar 

  • Park S, Baker JO, Himmel ME, Parilla PA, Johnson DK (2010) Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance. Biotechnol Biofuels 3:10

    PubMed  PubMed Central  Google Scholar 

  • Patil SKR, Heltzel J, Lund CRF (2012) Comparison of structural features of humins formed catalytically from glucose, fructose, and 5-hydroxymethylfurfuraldehyde. Energy Fuels 26:5281–5293

    CAS  Google Scholar 

  • Rabemanolontsoa H, Saka S (2013) Comparative study on chemical composition of various biomass species. RSC Adv 3:3946–3956

    CAS  Google Scholar 

  • Reis D, Vian BCR (2004) Helicoidal pattern in secondary cell walls and possible role of xylans in their construction. Biology 327:785–790

    CAS  Google Scholar 

  • Saito T, Kimura S, Nishiyama Y, Isogai A (2007) Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromol 8:2485–2491

    CAS  Google Scholar 

  • Salmén L, Burgert I (2009) Cell wall features with regard to mechanical performance. a review. COST Action E35 2004–2008: wood machining—micromechanics and fracture. Holzforschung 63:121–129

    Google Scholar 

  • Sarkanen KV (1961) The chemistry of delignification in pulp bleaching. Wood Chem Symp Proc 219–231

  • Savitzky A, Golay MJE (1964) Smoothing and differentiation of data by simplified least squares procedures. Anal Chem 36:1627–1639

    CAS  Google Scholar 

  • Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Templeton D, Crocker D (2008) National Renewable Energy Laboratory Technical Report NREL/TP-510-42618

  • Srebotnik E, Messner K (1994) A simple method that uses differential staining and light microscopy to assess the selectivity of wood delignification by white rot fungi. Appl Environ Microbiol 60:1383–1386

    CAS  PubMed  PubMed Central  Google Scholar 

  • Terashima N, Kitano K, Kojima M, Yoshida M, Yamamoto H, Westermark U (2009) Nanostructural assembly of cellulose, hemicellulose, and lignin in the middle layer of secondary wall of ginkgo tracheid. J Wood Sci 55:409–416

    CAS  Google Scholar 

  • Terrett OM, Lyczakowski JJ, Yu L, Iuga D, Franks WT, Brown SP, Dupree R, Dupree P (2019) Molecular architecture of softwood revealed by solid-state NMR. Nat Commun 10:4978

    PubMed  PubMed Central  Google Scholar 

  • Wada M, Okano T, Sugiyama J (1997) Synchrotron-radiated X-ray and neutron diffraction study of native cellulose. Cellulose 4:221–232

    CAS  Google Scholar 

  • Wang K, Liu X, Tan Y, Zhang W, Zhang S, Li J (2019) Two-dimensional membrane and three-dimensional bulk aerogel materials via top-down wood nanotechnology for multibehavioral and reusable oil/water separation. Chem Eng J 371:769–780

    CAS  Google Scholar 

  • Wayman M, Obiaga TI (1974) The modular structure of lignin. Can J Chem 52:2102–2110

    CAS  Google Scholar 

  • West E, MacInnes AS, Hibbert H (1943) Studies on lignin and related compounds. LXIX. Isolation of 1-(4-Hydroxy-3-methoxyphenyl)-2-propanone and 1-Ethoxy-1-(4-hydroxy-3-methoxyphenyl)-2-propanone from the ethanolysis products of spruce wood. J Am Chem Soc 65:1187e92

  • Wise LE, Murphy M, D’Addieco A (1946) A chlorite holocellulose, its fractionation and bearing on summative wood analysis and studies on the hemicelluloses. Pap Trade J 122:35

    CAS  Google Scholar 

  • Zhai Q, Li F, Wang F, Xu J, Jiang J, Cai Z (2018) Liquefaction of poplar biomass for value-added platform chemicals. Cellulose 25:4663–4675

    CAS  Google Scholar 

  • Zhao T, Zhang Y, Zhao G, Chen X, Han L, Xiao W (2018) Impact of biomass feedstock variability on acid-catalyzed alcoholysis performance. Fuel Process Technol 180:14–22

    CAS  Google Scholar 

  • Zsigmondy R, Scherrer P (1912) Bestimmung der inneren Struktur und der Größe von Kolloidteilchen mittels Röntgenstrahlen. Kolloidchemie Ein Lehrbuch 277:387–409

    Google Scholar 

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Acknowledgments

The authors sincerely appreciate Mr. Adachi of Kyoto University for providing the wood samples. This research study was jointly supported by JSPS a Grant-in-Aid for Scientific Research (Grant number 21J13235) and a Grant-in-Aid for Challenging Exploratory Research (KAKENHI, 22K19203).

Funding

This work was supported in part by the Japan Society for the Promotion of Science (JSPS) Grant-in-Aid for JSPS fellows (Grant number 21J13235) and a Grant-in-Aid for Challenging Exploratory Research (KAKENHI, 22K19203).

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Authors and Affiliations

  1. Department of Symbiotic Science of Environment and Natural Resources, The United Graduate School of Agricultural Science, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-Cho, Fuchu, Tokyo, 183-8509, Japan

    Seiya Hirano & Tatsuki Kurei

  2. Institute of Agriculture, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-Cho, Fuchu, Tokyo, 183-8509, Japan

    Satoshi Nakaba, Ryo Funada & Yoshiki Horikawa

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  1. Seiya Hirano
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  2. Tatsuki Kurei
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  3. Satoshi Nakaba
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  4. Ryo Funada
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  5. Yoshiki Horikawa
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Contributions

SH and YH carried out the chemical treatments and hierarchical structural assessments. TK carried out the X-ray diffraction analysis. SN and RF carried out the anatomical structural analysis. All authors read and approved the final manuscript.

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Correspondence to Yoshiki Horikawa.

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Hirano, S., Kurei, T., Nakaba, S. et al. Elucidation of alcoholysis for the preparation of lignin-free wood sections from Cryptomeria japonica. Cellulose 30, 6589–6600 (2023). https://doi.org/10.1007/s10570-023-05291-9

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