DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Nanoscale FTIR and Mechanical Mapping of Plant Cell Walls for Understanding Biomass Deconstruction

Abstract

Nano-FTIR and PeakForce quantitative nanomechanical mapping (PF QNM) are new AFM-based techniques that can be applied to plant tissues to get high-resolution spatial distribution of features that are unavailable from bulk characterization. This can be useful for finding changes to plant cell walls by processing technologies, mutations, or the environment. Three poplar hardwoods of varying recalcitrance and composition (high lignin, low lignin, and mutant) were investigated by nano-FTIR and PF QNM. Bulk characterization was carried out by conventional FTIR and NMR of isolated cellulose, hemicelluloses, and lignin. We found that in nano-FTIR spectra of secondary cell walls (SCW) and compound middle lamella (CML), 1162 and 1269 cm–1 could distinctly identify polysaccharides and lignin, respectively. Spatial variability in the content of polysaccharides and lignin was significantly larger in CML than SCW for all three poplars. Cellulose has a disordered structure in CML in comparison to SCW. PF QNM showed that SCW had a higher modulus of elasticity than CML due to the presence of crystalline cellulose in SCW. Differences in the physicochemical properties between the SCW and CML of plants can be probed at nanoscale by these techniques.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [2]; ORCiD logo [3];  [4];  [4]; ORCiD logo [1]; ORCiD logo [5]
  1. Biosciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
  2. Faculty of Forestry, Technical University in Zvolen, 96001 Zvolen, Slovakia
  3. Faculty of Wood Science and Technology, Technical University in Zvolen, 96001 Zvolen, Slovakia
  4. Attocube Systems AG, Eglfinger Weg 2, 85540 Haar, Germany
  5. Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, Tennessee 37996, United States, Joint Institute of Biological Sciences, Biosciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States, Center for Renewable Carbon, Department of Forestry, Wildlife, and Fisheries, University of Tennessee Institute of Agriculture, Knoxville, Tennessee 37996, United States
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1971697
Alternate Identifier(s):
OSTI ID: 1846533; OSTI ID: 1848052
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Published Article
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Name: ACS Sustainable Chemistry & Engineering Journal Volume: 10 Journal Issue: 9; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; Plant cell walls; PF QNM; FTIR; Nano-FTIR; NMR; Cellulose; Hemicellulose; Lignin; Populus trichocarpa; Cells; Carbohydrates; Biopolymers; Organic polymers

Citation Formats

Bhagia, Samarthya, Ďurkovič, Jaroslav, Lagaňa, Rastislav, Kardošová, Monika, Kačík, František, Cernescu, Adrian, Schäfer, Philip, Yoo, Chang Geun, and Ragauskas, Arthur J. Nanoscale FTIR and Mechanical Mapping of Plant Cell Walls for Understanding Biomass Deconstruction. United States: N. p., 2022. Web. doi:10.1021/acssuschemeng.1c08163.
Bhagia, Samarthya, Ďurkovič, Jaroslav, Lagaňa, Rastislav, Kardošová, Monika, Kačík, František, Cernescu, Adrian, Schäfer, Philip, Yoo, Chang Geun, & Ragauskas, Arthur J. Nanoscale FTIR and Mechanical Mapping of Plant Cell Walls for Understanding Biomass Deconstruction. United States. https://doi.org/10.1021/acssuschemeng.1c08163
Bhagia, Samarthya, Ďurkovič, Jaroslav, Lagaňa, Rastislav, Kardošová, Monika, Kačík, František, Cernescu, Adrian, Schäfer, Philip, Yoo, Chang Geun, and Ragauskas, Arthur J. Tue . "Nanoscale FTIR and Mechanical Mapping of Plant Cell Walls for Understanding Biomass Deconstruction". United States. https://doi.org/10.1021/acssuschemeng.1c08163.
@article{osti_1971697,
title = {Nanoscale FTIR and Mechanical Mapping of Plant Cell Walls for Understanding Biomass Deconstruction},
author = {Bhagia, Samarthya and Ďurkovič, Jaroslav and Lagaňa, Rastislav and Kardošová, Monika and Kačík, František and Cernescu, Adrian and Schäfer, Philip and Yoo, Chang Geun and Ragauskas, Arthur J.},
abstractNote = {Nano-FTIR and PeakForce quantitative nanomechanical mapping (PF QNM) are new AFM-based techniques that can be applied to plant tissues to get high-resolution spatial distribution of features that are unavailable from bulk characterization. This can be useful for finding changes to plant cell walls by processing technologies, mutations, or the environment. Three poplar hardwoods of varying recalcitrance and composition (high lignin, low lignin, and mutant) were investigated by nano-FTIR and PF QNM. Bulk characterization was carried out by conventional FTIR and NMR of isolated cellulose, hemicelluloses, and lignin. We found that in nano-FTIR spectra of secondary cell walls (SCW) and compound middle lamella (CML), 1162 and 1269 cm–1 could distinctly identify polysaccharides and lignin, respectively. Spatial variability in the content of polysaccharides and lignin was significantly larger in CML than SCW for all three poplars. Cellulose has a disordered structure in CML in comparison to SCW. PF QNM showed that SCW had a higher modulus of elasticity than CML due to the presence of crystalline cellulose in SCW. Differences in the physicochemical properties between the SCW and CML of plants can be probed at nanoscale by these techniques.},
doi = {10.1021/acssuschemeng.1c08163},
journal = {ACS Sustainable Chemistry & Engineering},
number = 9,
volume = 10,
place = {United States},
year = {Tue Feb 22 00:00:00 EST 2022},
month = {Tue Feb 22 00:00:00 EST 2022}
}

Works referenced in this record:

Near Infrared Spectroscopy and Chemometrics for Predicting Specific Gravity and Flexural Modulus of Elasticity of Pinus spp. Veneers
journal, January 2010

  • Carneiro, Mayara Elita; Magalhães, Washington Luiz Esteves; de Muñiz, Graciela I. B.
  • Journal of Near Infrared Spectroscopy, Vol. 18, Issue 6
  • DOI: 10.1255/jnirs.911

Reducing end groups in brich xylan and their alkaline degradation
journal, January 1977

  • Johansson, M. H.; Samuelson, O.
  • Wood Science and Technology, Vol. 11, Issue 4
  • DOI: 10.1007/BF00356924

Review of the most common pre-processing techniques for near-infrared spectra
journal, November 2009

  • Rinnan, Åsmund; Berg, Frans van den; Engelsen, Søren Balling
  • TrAC Trends in Analytical Chemistry, Vol. 28, Issue 10
  • DOI: 10.1016/j.trac.2009.07.007

Ultrastructural Changes in the Compound Middle Lamella of Pinus thunbergii During Lignification and Lignin Removal
journal, April 2000

  • Hafrén, Jonas; Fujino, Takeshi; Itoh, Takao
  • Holzforschung, Vol. 54, Issue 3
  • DOI: 10.1515/HF.2000.040

Natural genetic variability reduces recalcitrance in poplar
journal, May 2016

  • Bhagia, Samarthya; Muchero, Wellington; Kumar, Rajeev
  • Biotechnology for Biofuels, Vol. 9, Issue 1
  • DOI: 10.1186/s13068-016-0521-2

Nanoscale optical and structural characterisation of silk
journal, January 2019

  • Ryu, Meguya; Honda, Reo; Cernescu, Adrian
  • Beilstein Journal of Nanotechnology, Vol. 10
  • DOI: 10.3762/bjnano.10.93

Population-level approaches reveal novel aspects of lignin biosynthesis, content, composition and structure
journal, April 2019

  • Tuskan, Gerald A.; Muchero, Wellington; Tschaplinski, Timothy J.
  • Current Opinion in Biotechnology, Vol. 56
  • DOI: 10.1016/j.copbio.2019.02.017

In situ plant materials hyperspectral imaging by multimodal scattering near-field optical microscopy
journal, June 2021


A comparison of kraft, PS, kraft-AQ and kraft-NaBH4 pulps of Brutia pine
journal, March 2008


Heterogeneity of lignin concentration in cell corner middle lamella of white birch and black spruce
journal, April 1996

  • Tirumalai, V. C.; Agarwal, U. P.; Obst, J. R.
  • Wood Science and Technology, Vol. 30, Issue 2
  • DOI: 10.1007/BF00224961

The ultrastructure of the middle lamella region in resin canal tissue isolated from slash pine holocellulose
journal, January 1973

  • Kibblewhite, R. P.; Thompson, N. S.
  • Wood Science and Technology, Vol. 7, Issue 2
  • DOI: 10.1007/BF00351154

Variability in surface polarity of wood by means of AFM adhesion force mapping
journal, September 2014

  • Frybort, Stephan; Obersriebnig, Michael; Müller, Ulrich
  • Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 457
  • DOI: 10.1016/j.colsurfa.2014.05.055

Characterization of an acetylated heteroxylan from Eucalyptus globulus Labill
journal, March 2003


Characterization of acetylated 4-O-methylglucuronoxylan isolated from aspen employing 1H and 13C NMR spectroscopy
journal, December 2000


Infrared Nanospectroscopy Reveals the Chemical Nature of Pit Membranes in Water-Conducting Cells of the Plant Xylem
journal, June 2018

  • Pereira, Luciano; Flores-Borges, Denisele N. A.; Bittencourt, Paulo R. L.
  • Plant Physiology, Vol. 177, Issue 4
  • DOI: 10.1104/pp.18.00138

Calibration of rectangular atomic force microscope cantilevers
journal, October 1999

  • Sader, John E.; Chon, James W. M.; Mulvaney, Paul
  • Review of Scientific Instruments, Vol. 70, Issue 10
  • DOI: 10.1063/1.1150021

The hydrogen bond network in I β cellulose as observed by infrared spectrometry
journal, May 2000


Bioinspired lignocellulosic films to understand the mechanical properties of lignified plant cell walls at nanoscale
journal, March 2017

  • Muraille, L.; Aguié-Béghin, V.; Chabbert, B.
  • Scientific Reports, Vol. 7, Issue 1
  • DOI: 10.1038/srep44065

Hydration properties of xylan-type structures: an FTIR study of xylooligosaccharides
journal, May 1998


FTIR studies of the changes in wood chemistry following decay by brown-rot and white-rot fungi
journal, October 2003


High-resolution genetic mapping of allelic variants associated with cell wall chemistry in Populus
journal, January 2015


Infrared and Raman spectroscopy of carbohydrates. Paper V. Normal coordinate analysis of cellulose I
journal, February 1975

  • Cael, J. J.; Gardner, K. H.; Koenig, J. L.
  • The Journal of Chemical Physics, Vol. 62, Issue 3
  • DOI: 10.1063/1.430558

Comparative evaluation of Populus variants total sugar release and structural features following pretreatment and digestion by two distinct biological systems
journal, November 2017

  • Thomas, Vanessa A.; Kothari, Ninad; Bhagia, Samarthya
  • Biotechnology for Biofuels, Vol. 10, Issue 1
  • DOI: 10.1186/s13068-017-0975-x

Effects of short-time vibratory ball milling on the shape of FT-IR spectra of wood and cellulose
journal, October 2004


Ultrastructure and Enzymatic Hydrolysis of Deuterated Switchgrass
journal, September 2018


Mechanical heterogeneity of dentin at different length scales as determined by AFM phase contrast
journal, December 2012


FTIR Nanospectroscopy Shows Molecular Structures of Plant Biominerals and Cell Walls
journal, August 2020


Characterisation of the Interfacial Adhesion of the Different Components in Wood–Plastic Composites with AFM
journal, July 2015

  • Effah, Bernard; Van Reenen, Albert; Meincken, Martina
  • Springer Science Reviews, Vol. 3, Issue 2
  • DOI: 10.1007/s40362-015-0032-8

Preserving Aryl Ether Linkages and Higher Yields of Isolated Lignin through Biomass Fibrillation
journal, December 2019


MWL fraction with a high concentration of lignin-carbohydrate linkages: Isolation and 2D NMR spectroscopic analysis
journal, January 2007

  • Balakshin, Mikhail Yu.; Capanema, Ewellyn A.; Chang, Hou-min
  • Holzforschung, Vol. 61, Issue 1
  • DOI: 10.1515/HF.2007.001

Comparing Mechanical Properties of Secondary Wall and Cell Corner Middle Lamella in Spruce Wood
journal, January 1997


The Structure of Cellulose II: A Revisit
journal, November 1995

  • Raymond, S.; Kvick, Aa.; Chanzy, H.
  • Macromolecules, Vol. 28, Issue 24
  • DOI: 10.1021/ma00128a063

The infrared spectra of crystalline polysaccharides. VIII. Xylans
journal, June 1962


Investigation of Lignin Polymer Models (DHP’s) by FTIR Spectroscopy
journal, January 1986


Sub-micron phase coexistence in small-molecule organic thin films revealed by infrared nano-imaging
journal, June 2014

  • Westermeier, Christian; Cernescu, Adrian; Amarie, Sergiu
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5101

Elastic modulus of the crystalline regions of cellulose polymorphs
journal, August 1995

  • Nishino, Takashi; Takano, Kiyofumi; Nakamae, Katsuhiko
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 33, Issue 11
  • DOI: 10.1002/polb.1995.090331110

Classification of Lignins from Different Botanical Origins by FT-IR Spectroscopy
journal, January 1991