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Title: Solid-State Nuclear Magnetic Resonance as a Tool to Probe the Impact of Mechanical Preprocessing on the Structure and Arrangement of Plant Cell Wall Polymers

Journal Article · · Frontiers in Plant Science
 [1];  [2];  [3];  [1]
  1. Univ. of California, Davis, CA (United States)
  2. Joint BioEnergy Institute (JBEI), Emeryville, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
  3. Joint BioEnergy Institute (JBEI), Emeryville, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Univ. of Adelaide, SA (Australia)

Efficient separation of the plant cell wall polymers during lignocellulose processing has been historically challenging due to insolubility of the polymers and their propensity for recalcitrant reassembly. Methods, such as “lignin first” extraction techniques, have advanced efficient biomass use, but the molecular mechanisms for recalcitrance remain enigmatic. Here, we discuss how solid-state Nuclear Magnetic Resonance (NMR) approaches report on the 3D organization of cellulose, xylan, and lignin in the plant cell wall. Recent results illustrate that the organization of these polymers varies across biomass sources and sample preparation methods, with even minimal physical processing causing significant effects. These structural differences contribute to variable extraction efficiencies for bioproducts after downstream processing. We propose that solid-state NMR methods can be applied to follow biomass processing, providing an understanding of the polymer rearrangements that can lead to poor yields for the desired bioproducts. The utility of the technique is illustrated for mechanical processing using lab-scale vibratory ball milling ofSorghum bicolor.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
2470631
Journal Information:
Frontiers in Plant Science, Journal Name: Frontiers in Plant Science Vol. 12; ISSN 1664-462X
Publisher:
Frontiers Research FoundationCopyright Statement
Country of Publication:
United States
Language:
English

References (77)

3D Chemical Image using TOF-SIMS Revealing the Biopolymer Component Spatial and Lateral Distributions in Biomass journal October 2012
Characterization and analysis of the molecular weight of lignin for biorefining studies journal June 2014
The current and emerging sources of technical lignins and their applications: Sources of Technical Lignins journal July 2018
The structure of native cellulose journal October 1974
Future prospects of delignification pretreatments for the lignocellulosic materials to produce second generation bioethanol journal February 2019
NMRPipe: A multidimensional spectral processing system based on UNIX pipes journal November 1995
Carbon-13 NMR distinction between categories of molecular order and disorder in cellulose journal June 1995
Chemical diversity of lignin degradation products revealed by matrix-optimized MALDI mass spectrometry journal July 2019
Effects of ball milling on the structure of cotton cellulose journal January 2019
Ultrafine grinding of poplar biomass: effect of particle morphology on the liquefaction of biomass for methyl glycosides and phenolics journal March 2019
Assignment of non-crystalline forms in cellulose I by CP/MAS 13C NMR spectroscopy journal November 1998
Understanding the influences of different pretreatments on recalcitrance of Populus natural variants journal October 2018
Exploring the conformational space of amorphous cellulose using NMR chemical shifts journal October 2012
Covalent interactions between lignin and hemicelluloses in plant secondary cell walls journal April 2019
Effect of mechanical activation on structure changes and reactivity in further chemical modification of lignin journal October 2016
The effect of ball milling on birch, pine, reed, walnut shell enzymatic hydrolysis recalcitrance and the structure of the isolated residual enzyme lignin journal September 2021
Fast pyrolysis with fractional condensation of lignin-rich digested stillage from second-generation bioethanol production journal January 2020
Plant cell wall polymers as precursors for biofuels journal June 2010
Solid-state NMR of plant and fungal cell walls: A critical review journal June 2020
Effects of Pectin Molecular Weight Changes on the Structure, Dynamics, and Polysaccharide Interactions of Primary Cell Walls of Arabidopsis thaliana : Insights from Solid-State NMR journal August 2017
Direct Determination of Hydroxymethyl Conformations of Plant Cell Wall Cellulose Using 1 H Polarization Transfer Solid-State NMR journal December 2017
Selective One-Dimensional 13 C– 13 C Spin-Diffusion Solid-State Nuclear Magnetic Resonance Methods to Probe Spatial Arrangements in Biopolymers Including Plant Cell Walls, Peptides, and Spider Silk journal October 2020
On the Effect of Hot-Water Pretreatment in Sulfur-Free Pulping of Aspen and Wheat Straw journal December 2019
Approaches for More Efficient Biological Conversion of Lignocellulosic Feedstocks to Biofuels and Bioproducts journal April 2019
Structure and Interactions of Plant Cell-Wall Polysaccharides by Two- and Three-Dimensional Magic-Angle-Spinning Solid-State NMR journal February 2011
Pectin–Cellulose Interactions in the Arabidopsis Primary Cell Wall from Two-Dimensional Magic-Angle-Spinning Solid-State Nuclear Magnetic Resonance journal November 2012
Structure and Dynamics of Brachypodium Primary Cell Wall Polysaccharides from Two-Dimensional 13 C Solid-State Nuclear Magnetic Resonance Spectroscopy journal April 2014
Probing the Molecular Architecture of Arabidopsis thaliana Secondary Cell Walls Using Two- and Three-Dimensional 13 C Solid State Nuclear Magnetic Resonance Spectroscopy journal March 2015
Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources journal February 2013
What the X-Ray Tells Us of the Structure of Cellulose journal February 1929
X-Ray Studies of Crystallite Orientation in Cellulose Fibers Natural Fibers journal January 1935
Crystal Structure and Hydrogen-Bonding System in Cellulose Iβ from Synchrotron X-ray and Neutron Fiber Diffraction journal August 2002
Water–Polysaccharide Interactions in the Primary Cell Wall of Arabidopsis thaliana from Polarization Transfer Solid-State NMR journal July 2014
Determination of Through-Bond Carbon−Carbon Connectivities in Solid-State NMR Using the INADEQUATE Experiment journal August 1997
Through-Bond Carbon−Carbon Connectivities in Disordered Solids by NMR journal December 1999
Solid-State Selective 13 C Excitation and Spin Diffusion NMR To Resolve Spatial Dimensions in Plant Cell Walls journal February 2012
Studies of microstructure in native celluloses using solid-state carbon-13 NMR journal August 1984
Packing Analysis of Carbohydrates and Polysaccharides. III. Valonia Cellulose and Cellulose II journal July 1974
Folding of xylan onto cellulose fibrils in plant cell walls revealed by solid-state NMR journal December 2016
Lignin-polysaccharide interactions in plant secondary cell walls revealed by solid-state NMR journal January 2019
Molecular architecture of softwood revealed by solid-state NMR journal October 2019
A grass-specific cellulose–xylan interaction dominates in sorghum secondary cell walls journal November 2020
An even pattern of xylan substitution is critical for interaction with cellulose in plant cell walls journal October 2017
Influence of amorphous cellulose on mechanical, thermal, and hydrolytic degradation of poly(lactic acid) biocomposites journal July 2020
Solution-state 2D NMR of ball-milled plant cell wall gels in DMSO-d6/pyridine-d5 journal January 2010
A review of whole cell wall NMR by the direct-dissolution of biomass journal January 2016
Biomass pretreatment using deep eutectic solvents from lignin derived phenols journal January 2018
Cellulolytic enzyme-aided extraction of hemicellulose from switchgrass and its characteristics journal January 2019
An improved catalytic pyrolysis concept for renewable aromatics from biomass involving a recycling strategy for co-produced polycyclic aromatic hydrocarbons journal January 2019
Comparing chemical composition and lignin structure of Miscanthus x giganteus and Miscanthus nagara harvested in autumn and spring and separated into stems and leaves journal January 2020
Application of quantitative 31P NMR in biomass lignin and biofuel precursors characterization journal January 2011
Molecular domains of the cellulose/xyloglucan network in the cell walls of higher plants journal December 1999
Through-space contributions to two-dimensional double-quantum J correlation NMR spectra of magic-angle-spinning solids journal May 2005
Nanostructure of cellulose microfibrils in spruce wood journal November 2011
Sensitivity-enhanced solid-state NMR detection of expansin's target in plant cell walls journal September 2013
Redesigning plant cell walls for the biomass-based bioeconomy journal August 2020
On the Quantification of Lignin Hydroxyl Groups With 31 P and 13 C NMR Spectroscopy journal April 2015
NMRFAM-SPARKY: enhanced software for biomolecular NMR spectroscopy journal December 2014
Solid-state 13C-NMR spectroscopy shows that the xyloglucans in the primary cell walls of mung bean (Vigna radiata L.) occur in different domains: a new model for xyloglucan-cellulose interactions in the cell wall journal January 2004
Solid-state NMR investigations of cellulose structure and interactions with matrix polysaccharides in plant primary cell walls journal September 2015
A Revised Architecture of Primary Cell Walls Based on Biomechanical Changes Induced by Substrate-Specific Endoglucanases journal February 2012
Cellulose-Pectin Spatial Contacts Are Inherent to Never-Dried Arabidopsis Primary Cell Walls: Evidence from Solid-State Nuclear Magnetic Resonance journal June 2015
Evolution of xylan substitution patterns in gymnosperms and angiosperms: implications for xylan interaction with cellulose journal June 2016
The Structure of Plant Cell Walls: I. The Macromolecular Components of the Walls of Suspension-cultured Sycamore Cells with a Detailed Analysis of the Pectic Polysaccharides journal January 1973
The Structure of Plant Cell Walls: III. A Model of the Walls of Suspension-cultured Sycamore Cells Based on the Interconnections of the Macromolecular Components journal January 1973
Arabinosyl Deacetylase Modulates the Arabinoxylan Acetylation Profile and Secondary Wall Formation journal March 2019
An update on enzymatic cocktails for lignocellulose breakdown journal July 2018
The plant cell wall: Biosynthesis, construction, and functions journal January 2021
Unlocking the potential of lignocellulosic biomass through plant science journal October 2015
Hemicelluloses journal June 2010
Crystallinity of Cellulose and Its Significance for the Fiber Properties journal June 1950
An automated growth enclosure for metabolic labeling of Arabidopsis thaliana with 13C-carbon dioxide - an in vivo labeling system for proteomics and metabolomics research journal January 2011
Progress in understanding and overcoming biomass recalcitrance: a BioEnergy Science Center (BESC) perspective journal November 2017
Current Understanding of the Correlation of Lignin Structure with Biomass Recalcitrance journal November 2016
Direct Measurement of Plant Cellulose Microfibril and Bundles in Native Cell Walls journal April 2020
Analysis of Cellulose and Lignocellulose Materials by Raman Spectroscopy: A Review of the Current Status journal April 2019
Characterization of Lignin Compounds at the Molecular Level: Mass Spectrometry Analysis and Raw Data Processing journal January 2021