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Probing cellulose structures with vibrational spectroscopy

Journal Article · · Cellulose
 [1];  [2];  [2];  [2];  [2];  [2];  [3];  [2]
  1. Pennsylvania State Univ., University Park, PA (United States); The Pennsylvania State University
  2. Pennsylvania State Univ., University Park, PA (United States)
  3. Univ. of Texas, El Paso, TX (United States)
This paper reviews principles, data interpretations, and applications of vibrational spectroscopic methods used for analysis of cellulose in the isolated state and in plant cell walls or lignocellulose biomass. The paper begins with reviewing the crystalline structures of crystalline cellulose polymorphs and the principles of three different vibrational spectroscopy methods—infrared (IR), Raman, and sum frequency generation (SFG)—complemented with density functional theory calculations. Then, it discusses the vibrational modes of crystalline celluloses, how the chain orientation in crystalline domain is analyzed in each method, and how the concentration and spatial distribution of crystalline cellulose domains interspersed in amorphous matrices are manifested or analyzed differently in these three methods. Finally, the paper discusses examples of analyzing crystalline cellulose in plant cell walls or lignocellulose biomass with IR, Raman, and SFG including spectroscopic imaging. One review cannot cover all vibrational spectroscopy literatures on cellulose; this review aims at providing tutorial information, using selected literatures and experimental data, needed to interpret nano-, meso-, and micro-scale structures of cellulose in plant cell walls and lignocellulose biomass.
Research Organization:
Pennsylvania State Univ., University Park, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0001090
OSTI ID:
1634200
Journal Information:
Cellulose, Journal Name: Cellulose Journal Issue: 1 Vol. 26; ISSN 0969-0239
Publisher:
SpringerCopyright Statement
Country of Publication:
United States
Language:
English

References (170)

A Chemist's Guide to Density Functional Theory book July 2001
Evaluating cell wall structure and composition of developing cotton fibers using Fourier transform infrared spectroscopy and thermogravimetric analysis journal January 2007
Semiempirical GGA-type density functional constructed with a long-range dispersion correction journal January 2006
Vibrational frequency scale factors for density functional theory and the polarization consistent basis sets journal July 2012
Infrared spectrum and crystal structure of cellulose journal July 1957
Almost Pure Iα Cellulose in the Cell Wall of Glaucocystis journal October 1999
Principal Component Analysis book January 1986
Control of thickness of collenchyma cell walls by pectins journal May 1992
Solid-state 13C-NMR study of conformations of oligosaccharides and cellulose: Conformation of CH2OH group about the exo-cyclic C-C bond journal September 1983
Correlation of O-H stretching frequencies and O-H…O hydrogen bond lengths in minerals journal August 1999
Raman imaging to investigate ultrastructure and composition of plant cell walls: distribution of lignin and cellulose in black spruce wood (Picea mariana) journal June 2006
Microfibril orientation across the secondary cell wall of Radiata pine tracheids journal April 2005
A survey of cellulose microfibril patterns in dividing, expanding, and differentiating cells of Arabidopsis thaliana journal October 2013
Moisture uptake in native cellulose – the roles of different hydrogen bonds: a dynamic FT-IR study using Deuterium exchange journal March 2006
Cellulose I crystallinity determination using FT–Raman spectroscopy: univariate and multivariate methods journal May 2010
Quantum mechanical modeling of the structures, energetics and spectral properties of Iα and Iβ cellulose journal February 2013
Cellulose microfibril orientation in onion (Allium cepa L.) epidermis studied by atomic force microscopy (AFM) and vibrational sum frequency generation (SFG) spectroscopy journal December 2013
Cellulose polymorphism study with sum-frequency-generation (SFG) vibration spectroscopy: identification of exocyclic CH2OH conformation and chain orientation journal April 2013
Visualization of the nanoscale pattern of recently-deposited cellulose microfibrils and matrix materials in never-dried primary walls of the onion epidermis journal July 2013
Vibrational sum-frequency-generation (SFG) spectroscopy study of the structural assembly of cellulose microfibrils in reaction woods journal June 2014
Comprehensive analysis of cellulose content, crystallinity, and lateral packing in Gossypium hirsutum and Gossypium barbadense cotton fibers using sum frequency generation, infrared and Raman spectroscopy, and X-ray diffraction journal January 2015
Does cellulose II exist in native alga cell walls? Cellulose structure of Derbesia cell walls studied with SFG, IR and XRD journal October 2015
Probing crystallinity of never-dried wood cellulose with Raman spectroscopy journal October 2015
Comparative physical and chemical analyses of cotton fibers from two near isogenic upland lines differing in fiber wall thickness journal April 2017
Effects of mechanical stretching on average orientation of cellulose and pectin in onion epidermis cell wall: A polarized FT-IR study journal May 2017
Comparison and validation of Fourier transform infrared spectroscopic methods for monitoring secondary cell wall cellulose from cotton fibers journal November 2017
An evaluation of the structures of cellulose generated by the CHARMM force field: comparisons to in planta cellulose journal April 2018
Use of FT-IR Spectra and PCA to the Bulk Characterization of Cell Wall Residues of Fruits and Vegetables Along a Fraction Process journal December 2012
Effects of Delignification on Crystalline Cellulose in Lignocellulose Biomass Characterized by Vibrational Sum Frequency Generation Spectroscopy and X-ray Diffraction journal May 2015
X-ray line broadening from filed aluminium and wolfram journal January 1953
Band assignments in the raman spectra of celluloses journal February 1987
Surface and interface stress effects in thin films journal May 1994
Investigation of macromolecule orientation in dry and hydrated walls of single onion epidermal cells by FTIR microspectroscopy journal June 1997
The hydrogen bond network in I β cellulose as observed by infrared spectrometry journal May 2000
Conformation and packing of various crystalline cellulose fibers journal November 2001
FT-IR study of plant cell wall model compounds: pectic polysaccharides and hemicelluloses journal October 2000
Fourier transform Raman and infrared spectroscopy of pectins journal October 2003
Spatial resolution in infrared microspectroscopic imaging of tissues journal July 2006
A critical review of analytical methods in pretreatment of lignocelluloses: Composition, imaging, and crystallinity journal January 2016
Qualitative and quantitative analysis of wood samples by Fourier transform infrared spectroscopy and multivariate analysis journal October 2010
Quantification of crystalline cellulose in lignocellulosic biomass using sum frequency generation (SFG) vibration spectroscopy and comparison with other analytical methods journal July 2012
Cellulose produced by Gluconacetobacter xylinus strains ATCC 53524 and ATCC 23768: Pellicle formation, post-synthesis aggregation and fiber density journal November 2015
New cellulose crystallinity estimation method that differentiates between organized and crystalline phases journal June 2018
Dehydration-induced physical strains of cellulose microfibrils in plant cell walls journal October 2018
Crystalline structure analysis of cellulose treated with sodium hydroxide and carbon dioxide by means of X-ray diffraction and FTIR spectroscopy journal October 2005
Characterization of the surface properties of xylan by FT-Raman spectroscopy and wicking technique journal December 2004
Improvement of plant based natural fibers for toughening green composites—Effect of load application during mercerization of ramie fibers journal December 2006
Formation of macromolecular lignin in ginkgo xylem cell walls as observed by field emission scanning electron microscopy journal September 2004
Wood formation in Angiosperms journal April 2010
Plant cell walls journal September 2017
Relationships between micro-fibrillar angle, mechanical properties and biochemical composition of flax fibers journal January 2013
Re-constructing our models of cellulose and primary cell wall assembly journal December 2014
Effects of short-time vibratory ball milling on the shape of FT-IR spectra of wood and cellulose journal October 2004
High-Resolution Field Emission Scanning Electron Microscopy (FESEM) Imaging of Cellulose Microfibril Organization in Plant Primary Cell Walls journal August 2017
Cellulose microfibril angle in the cell wall of wood fibres journal January 1999
Hydrogen-Bonding Network and OH Stretch Vibration of Cellulose: Comparison of Computational Modeling with Polarized IR and SFG Spectra journal November 2015
Multimodal Broadband Vibrational Sum Frequency Generation (MM-BB-V-SFG) Spectrometer and Microscope journal December 2015
Inhomogeneity of Cellulose Microfibril Assembly in Plant Cell Walls Revealed with Sum Frequency Generation Microscopy journal April 2018
Dependence of Sum Frequency Generation (SFG) Spectral Features on the Mesoscale Arrangement of SFG-Active Crystalline Domains Interspersed in SFG-Inactive Matrix: A Case Study with Cellulose in Uniaxially Aligned Control Samples and Alkali-Treated Secondary Cell Walls of Plants journal May 2017
Experimental and Theoretical Study of Azimuth Angle and Polarization Dependences of Sum-Frequency-Generation Vibrational Spectral Features of Uniaxially Aligned Cellulose Crystals journal August 2017
Distinguishing Surface versus Bulk Hydroxyl Groups of Cellulose Nanocrystals Using Vibrational Sum Frequency Generation Spectroscopy journal December 2017
Absence of Sum Frequency Generation in Support of Orthorhombic Symmetry of α-Chitin journal September 2016
Comparison of the Properties of Cellulose Nanocrystals and Cellulose Nanofibrils Isolated from Bacteria, Tunicate, and Wood Processed Using Acid, Enzymatic, Mechanical, and Oxidative Methods journal April 2014
Pectin–Cellulose Interactions in the Arabidopsis Primary Cell Wall from Two-Dimensional Magic-Angle-Spinning Solid-State Nuclear Magnetic Resonance journal November 2012
Lignin: Historical, Biological, and Materials Perspectives book November 1999
X-ray Structure of Mercerized Cellulose II at 1 Å Resolution journal June 2001
Polymorphism of Cellulose I Family:  Reinvestigation of Cellulose IV I journal July 2004
Molecular Directionality in Cellulose Polymorphs journal January 2006
Selective Detection of Crystalline Cellulose in Plant Cell Walls with Sum-Frequency-Generation (SFG) Vibration Spectroscopy journal July 2011
Effects of Plant Cell Wall Matrix Polysaccharides on Bacterial Cellulose Structure Studied with Vibrational Sum Frequency Generation Spectroscopy and X-ray Diffraction journal May 2014
Temperature-Dependent Changes in Hydrogen Bonds in Cellulose Iα Studied by Infrared Spectroscopy in Combination with Perturbation-Correlation Moving-Window Two-Dimensional Correlation Spectroscopy:  Comparison with Cellulose Iβ journal September 2007
Cellulose Nanocrystals: Chemistry, Self-Assembly, and Applications journal June 2010
Scaling Factors and Uncertainties for ab Initio Anharmonic Vibrational Frequencies journal July 2010
The evidence from infrared spectroscopy for hydrogen bonding: A case history of the correlation and interpretation of data journal June 1957
Crystal Structure and Hydrogen-Bonding System in Cellulose Iβ from Synchrotron X-ray and Neutron Fiber Diffraction journal August 2002
Crystal Structure and Hydrogen Bonding System in Cellulose I α from Synchrotron X-ray and Neutron Fiber Diffraction journal November 2003
Characterization of Arabidopsis thaliana Lines with Altered Seed Storage Protein Profiles Using Synchrotron-Powered FT-IR Spectromicroscopy journal January 2013
Ab Initio Studies of Cellulose I: Crystal Structure, Intermolecular Forces, and Interactions with Water journal May 2011
Ab Initio Study of Structure and Interconversion of Native Cellulose Phases journal September 2011
Sum-Frequency-Generation Vibration Spectroscopy and Density Functional Theory Calculations with Dispersion Corrections (DFT-D2) for Cellulose Iα and Iβ journal May 2013
Characterization of Starch Polymorphic Structures Using Vibrational Sum Frequency Generation Spectroscopy journal February 2014
Vibrational Density of States of Strongly H-Bonded Interfacial Water: Insights from Inelastic Neutron Scattering and Theory journal May 2014
Transformation of Valonia cellulose crystals by an alkaline hydrothermal treatment journal June 1990
Raman Spectral Evidence for Molecular Orientation in Native Cellulosic Fibers journal November 1980
Quantification of cellulose forms in complex cellulose materials: a chemometric model journal January 2001
Random quasi-phase-matching in bulk polycrystalline isotropic nonlinear materials journal November 2004
Nanoscale movements of cellulose microfibrils in primary cell walls journal April 2017
Growth of the plant cell wall journal November 2005
Resonant soft X-ray scattering reveals cellulose microfibril spacing in plant primary cell walls journal August 2018
Progressive structural changes of Avicel, bleached softwood and bacterial cellulose during enzymatic hydrolysis journal October 2015
Comparative Structural and Computational Analysis Supports Eighteen Cellulose Synthases in the Plant Cellulose Synthesis Complex journal June 2016
Application of vibrational spectroscopy techniques to non-destructively monitor plant health and development journal January 2015
Cellulose nanomaterials review: structure, properties and nanocomposites journal January 2011
Probing crystal structure and mesoscale assembly of cellulose microfibrils in plant cell walls, tunicate tests, and bacterial films using vibrational Sum Frequency Generation (SFG) spectroscopy journal January 2014
In vitro synthesis of cellulose microfibrils by a membrane protein from protoplasts of the non-vascular plant Physcomitrella patens journal August 2015
Infrared and Raman Spectra of the Cellulose from the Cell Wall of Valonia ventricosa journal October 1970
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
Infrared and Raman spectroscopy of carbohydrates. Paper V. Normal coordinate analysis of cellulose I journal February 1975
Analytic Raman intensities from molecular electronic wave functions journal January 1986
Analytic evaluation and basis set dependence of intensities of infrared spectra journal February 1986
Differences between the exact sum-over-states and the canonical approximation for the calculation of static and dynamic hyperpolarizabilities journal October 1997
Capturing inhomogeneous broadening of the –CN stretch vibration in a Langmuir monolayer with high-resolution spectra and ultrafast vibrational dynamics in sum-frequency generation vibrational spectroscopy (SFG-VS) journal August 2013
Vibrational sum frequency generation digital holography journal June 2017
Nanostructure of cellulose microfibrils in spruce wood journal November 2011
Cellulose synthase complexes act in a concerted fashion to synthesize highly aggregated cellulose in secondary cell walls of plants journal September 2016
Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS) journal April 2005
New insights into plant cell walls by vibrational microspectroscopy journal September 2017
Order-of-magnitude estimates of the nonlinear optical susceptibility journal March 1999
Implementing the Theory of Sum Frequency Generation Vibrational Spectroscopy: A Tutorial Review journal May 2005
Optical phonons of small crystals journal January 1970
Cellulose orientation determines mechanical anisotropy in onion epidermis cell walls journal May 2006
Onion epidermis as a new model to study the control of growth anisotropy in higher plants journal August 2009
Solid-state NMR investigations of cellulose structure and interactions with matrix polysaccharides in plant primary cell walls journal September 2015
Secondary cell walls: biosynthesis and manipulation journal December 2015
Nonlinear optical scattering: The concept of effective susceptibility journal September 2004
Sum frequency generation scattering from the interface of an isotropic particle: Geometrical and chiral effects journal June 2007
Nonlinear Mie theory for second-harmonic and sum-frequency scattering journal April 2009
Separating surface structure and surface charge with second-harmonic and sum-frequency scattering journal December 2010
Quantitative analysis of lattice disorder and crystallite size in organic semiconductor thin films journal July 2011
Vibrational Sum Frequency Scattering from a Submicron Suspension journal December 2003
Van der Waals Density Functional for General Geometries journal June 2004
Fourier Transform Infrared Microspectroscopy Is a New Way to Look at Plant Cell Walls journal December 1992
Fourier-Transform Raman and Fourier-Transform Infrared Spectroscopy (An Investigation of Five Higher Plant Cell Walls and Their Components) journal December 1994
Real-Time Imaging of Cellulose Reorientation during Cell Wall Expansion in Arabidopsis Roots journal December 2009
A Revised Architecture of Primary Cell Walls Based on Biomechanical Changes Induced by Substrate-Specific Endoglucanases journal February 2012
Structure of Cellulose Microfibrils in Primary Cell Walls from Collenchyma journal November 2012
The anisotropy1 D604N Mutation in the Arabidopsis Cellulose Synthase1 Catalytic Domain Reduces Cell Wall Crystallinity and the Velocity of Cellulose Synthase Complexes journal March 2013
Monitoring Meso-Scale Ordering of Cellulose in Intact Plant Cell Walls Using Sum Frequency Generation Spectroscopy journal August 2013
Wide-Angle X-Ray Scattering and Solid-State Nuclear Magnetic Resonance Data Combined to Test Models for Cellulose Microfibrils in Mung Bean Cell Walls journal October 2013
Molecular Rigidity in Dry and Hydrated Onion Cell Walls journal October 1997
The Mechanical Properties and Molecular Dynamics of Plant Cell Wall Polysaccharides Studied by Fourier-Transform Infrared Spectroscopy journal September 2000
Cellulose-Pectin Spatial Contacts Are Inherent to Never-Dried Arabidopsis Primary Cell Walls: Evidence from Solid-State Nuclear Magnetic Resonance journal June 2015
A Structural Study of CESA1 Catalytic Domain of Arabidopsis Cellulose Synthesis Complex: Evidence for CESA Trimers journal November 2015
Functional Specialization of Cellulose Synthase Isoforms in a Moss Shows Parallels with Seed Plants journal August 2017
A Kinesin-Like Protein Is Essential for Oriented Deposition of Cellulose Microfibrils and Cell Wall Strength journal December 2002
The jiaoyao1 Mutant Is an Allele of korrigan1 That Abolishes Endoglucanase Activity and Affects the Organization of Both Cellulose Microfibrils and Microtubules in Arabidopsis journal June 2014
The Arabidopsis Cellulose Synthase Complex: A Proposed Hexamer of CESA Trimers in an Equimolar Stoichiometry journal December 2014
PROCUSTE1 Encodes a Cellulose Synthase Required for Normal Cell Elongation Specifically in Roots and Dark-Grown Hypocotyls of Arabidopsis journal December 2000
Spatial organization of cellulose microfibrils and matrix polysaccharides in primary plant cell walls as imaged by multichannel atomic force microscopy journal January 2016
Native Cellulose: A Composite of Two Distinct Crystalline Forms journal January 1984
A Molecular Description of Cellulose Biosynthesis journal June 2015
Cellulose Synthesis in Higher Plants journal November 2006
Time-Dependent Density Functional Theory journal June 2004
Cellulose polymorphs and physical properties of cotton fabrics processed with commercial textile mills for mercerization and liquid ammonia treatments journal March 2014
X-ray diffraction and FTIR investigations of cellulose deposition during cotton fiber development journal January 2017
Perturbation of Brachypodium distachyon CELLULOSE SYNTHASE A4 or 7 results in abnormal cell walls journal January 2013
Measuring the distribution of cellulose microfibril angles in primary cell walls by small angle X-ray scattering journal January 2014
Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance journal January 2010
Effect of mechanical disruption on the effectiveness of three reactors used for dilute acid pretreatment of corn stover Part 1: chemical and physical substrate analysis journal January 2014
In situ label-free imaging of hemicellulose in plant cell walls using stimulated Raman scattering microscopy journal November 2016
Modification of the nanostructure of lignocellulose cell walls via a non-enzymatic lignocellulose deconstruction system in brown rot wood-decay fungi journal July 2017
Plant Cell Walls book April 2010
Direct visualization of cross-links in the primary plant cell wall journal June 1990
Thermally Induced Crystal Transformation from Cellulose Iα to Iβ journal February 2003
Theory of optical second-harmonic and sum-frequency scattering from arbitrarily shaped particles journal January 2011
Rapid vibrational imaging with sum frequency generation microscopy journal January 2011
Spectral Characterization of Eucalyptus Wood journal November 2007
FT-Raman Spectroscopy of Wood: Identifying Contributions of Lignin and Carbohydrate Polymers in the Spectrum of Black Spruce (Picea Mariana) journal November 1997
Sum Frequency Generation Microscopy Study of Cellulose Fibers journal November 2011
Comparative Investigation of Fourier Transform Infrared (FT-IR) Spectroscopy and X-ray Diffraction (XRD) in the Determination of Cotton Fiber Crystallinity journal August 2012
Sum Frequency Generation Confocal Microscopy Observation of a Fish Scale journal January 2014
Quantum Chemical Calculation of Raman Intensities for Large Molecules: The Photoisomerization of [{Fe‘S 4 ’(PR 3 )} 2 (N 2 H 2 )] (‘S 42− = 1,2-bis(2-Mercaptophenylthio)-Ethane(2−)) journal February 2003
Plasma membrane H + ‐ ATP ase regulation is required for auxin gradient formation preceding phototropic growth journal September 2014
Effects and measurement of internal surface stresses in materials with ultrafine microstructures journal May 1991
Cellulose nanocrystals: synthesis, functional properties, and applications journal November 2015
PROCUSTE1 Encodes a Cellulose Synthase Required for Normal Cell Elongation Specifically in Roots and Dark-Grown Hypocotyls of Arabidopsis journal December 2000
FT-IR Examination of the Development of Secondary Cell Wall in Cotton Fibers journal January 2015
Recent Progress in Fourier Transform Infrared (FTIR) Spectroscopy Study of Compositional, Structural and Physical Attributes of Developmental Cotton Fibers journal January 2013
Measuring the distribution of cellulose microfibril angles in primary cell walls by small angle X-ray scattering text January 2014
Plasma Membrane H⁺ -Atpase Regulation Is Required For Auxin Gradient Formation Preceding Phototropic Growth text January 2014

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