Quantification of crystalline cellulose in lignocellulosic biomass using sum frequency generation (SFG) vibration spectroscopy and comparison with other analytical methods

Barnette, Anna L.; Lee, Christopher; Bradley, Laura C.; Schreiner, Edward P.; Park, Yong Bum; Shin, Heenae; Cosgrove, Daniel J.; Park, Sunkyu; Kim, Seong H.

doi:10.1016/j.carbpol.2012.04.014

Cited by 75 publications

(104 citation statements)

References 53 publications

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“…However, it is important to note that the isolation of cellulose microfibrils in these studies often involves harsh extraction methods that will affect the native cel- lulose structure (Somerville, 2006). A sum frequency generation (SFG) spectroscopy was recently used to detect the asymmetric distribution of C6H2 and O3H-O5 group in crystalline cellulose microfibrils (Hieu et al, 2011;Barnette et al, 2012). SFG is a desirable method to estimate the content of crystalline cellulose because there is no spectral interference from other cell wall matrix compounds such as hemicellulose and lignin and it does not require any chemical treatment of biological samples (Barnette et al, 2012).…”

Section: General Structure Of Cellulosementioning

confidence: 99%

“…A sum frequency generation (SFG) spectroscopy was recently used to detect the asymmetric distribution of C6H2 and O3H-O5 group in crystalline cellulose microfibrils (Hieu et al, 2011;Barnette et al, 2012). SFG is a desirable method to estimate the content of crystalline cellulose because there is no spectral interference from other cell wall matrix compounds such as hemicellulose and lignin and it does not require any chemical treatment of biological samples (Barnette et al, 2012). SFG can also detect subtle changes in cellulose ordering and packing in secondary cell wall in Arabidopsis inflorescence stem (Park et al, 2013).…”

Section: General Structure Of Cellulosementioning

confidence: 99%

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Cellulose Synthesis and Its Regulation

Bashline

Lei

et al. 2014

The Arabidopsis Book

122

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Cellulose, the most abundant biopolymer synthesized on land, is made of linear chains of β (1-4) linked D-glucose. As a major structural component of the cell wall, cellulose is important not only for industrial use but also for plant growth and development. Cellulose microfibrils are tethered by other cell wall polysaccharides such as hemicellulose, pectin, and lignin. In higher plants, cellulose is synthesized by plasma membrane-localized rosette cellulose synthase complexes. Despite the recent advances using a combination of molecular genetics, live cell imaging, and spectroscopic tools, many aspects of the cellulose synthesis remain a mystery. In this chapter, we highlight recent research progress towards understanding the mechanism of cellulose synthesis in Arabidopsis.

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Section: General Structure Of Cellulosementioning

confidence: 99%

Section: General Structure Of Cellulosementioning

confidence: 99%

Cellulose Synthesis and Its Regulation

Bashline

Lei

et al. 2014

The Arabidopsis Book

122

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“…[7][8][9][10][11][12] These various forms of SFG microscopy have been used to study a growing number of spatially heterogeneous samples, including patterned molecular monolayers on planar surfaces 7 , biomolecular microcrystals [13][14] and biofibers. 9,[15][16] Among the various forms of SFG microscopy, the point-scanning configuration with collinear excitation beams is attractive because the microscope layout is similar to a standard laser-scanning nonlinear optical microscope. 17 This configuration not only enables fast scanning capabilities with sub-micrometer lateral resolution, but also allows the simultaneous recording of images based on alternative forms of nonlinear optical contrast such as nonresonant second harmonic generation (SHG) 18 , which is especially useful when imaging microscopic structures with intrinsic non-centrosymmetry.…”

Section: Introductionmentioning

confidence: 99%

Polarization-Sensitive Sum-Frequency Generation Microscopy of Collagen Fibers

Han

Hsu

et al. 2015

J. Phys. Chem. B

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Point-scanning sum-frequency generation (SFG) microscopy enables the generation of images of collagen I fibers in tissues by tuning into specific vibrational resonances of the polypeptide. It is shown that when collagen-rich tissues are visualized near the 2954 cm -1 stretching vibration of methylene groups, the SFG image contrast is higher compared to the contrast seen in nonresonant second-harmonic generation (SHG) imaging.Polarization and spectrally resolved analysis of the SFG signal as a function of fiber orientation in the CH-stretching range of the vibrational spectrum enabled a comparative characterization of the achiral tensor elements of collagen's second-order susceptibility. This analysis reveals that selected on-resonance tensor elements are enhanced over other elements, giving rise to a much stronger anisotropy ρ of the signal for SFG ( ρ≈15 ) compared to SHG ( ρ≈3 ). The improved anisotropy of the vibrationally resonant signal contributes to the higher contrast seen in the SFG tissue images.

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“…Although XRD has been used widely to estimate cellulose crystallinity in secondary cell walls and lignocellulosic biomass, crystallinity measurements are inaccurate, as the value varies greatly with the data-fitting methods (Barnette et al, 2012). Likewise, spectral overlaps or interference from noncellulosic matrix polymers make it challenging to analyze cellulose structure in intact plant cell walls with 13 C-NMR and Raman and IR spectroscopy (Park et al, 2010).Sum frequency generation (SFG) spectroscopy has the potential to selectively detect crystalline cellulose without spectral interference from other wall components (Barnette et al, 2011(Barnette et al, , 2012. SFG is a nonlinear optical process that occurs in crystalline materials with a noncentrosymmetric structure or at interfaces (Chen et al, 2002).…”

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Monitoring Meso-Scale Ordering of Cellulose in Intact Plant Cell Walls Using Sum Frequency Generation Spectroscopy

et al. 2013

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Sum frequency generation (SFG) vibration spectroscopy can selectively detect crystalline cellulose without spectral interference from cell wall matrix components. Here, we show that the cellulose SFG spectrum is sensitive to cellulose microfibril alignment and packing within the cell wall. SFG intensity at 2,944 cm 21 correlated well with crystalline cellulose contents of various regions of the Arabidopsis (Arabidopsis thaliana) inflorescence, while changes in the 3,320/2,944 cm 21 intensity ratio suggest subtle changes in cellulose ordering as tissues mature. SFG analysis of two cellulose synthase mutants (irx1/cesa8 and irx3/cesa7) indicates a reduction in cellulose content without evidence of altered cellulose structure. In primary cell walls of Arabidopsis, cellulose exhibited a characteristic SFG peak at 2,920 and 3,320 cm 21, whereas in secondary cell walls, it had peaks at 2,944 and 3,320 cm 21. Starch (amylose) gave an SFG peak at 2,904 cm 21 (CH methine) whose intensity increased with light exposure prior to harvest. Selective removal of matrix polysaccharides from primary cell walls by acid hydrolysis resulted in an SFG spectrum resembling that of secondary wall cellulose. Our results show that SFG spectroscopy is sensitive to the ordering of cellulose microfibrils in plant cell walls at the meso scale (nm to mm) that is important for cell wall architecture but cannot be probed by other spectroscopic or diffraction techniques.Cellulose is a major component of lignocellulosic biomass as well as the most abundant biopolymer on Earth (Pauly and Keegstra, 2008). Chemically, cellulose is described as a linear polymer of 1→4-linked b-Dglucopyranose units. In plant cell walls, cellulose commonly exists in the form of approximately 3-nm-wide microfibrils containing numerous parallel glucan chains (variously estimated as 18-36) closely packed to form a highly ordered, or crystalline, structure (Doblin et al., 2002;Nishiyama et al., 2002;Somerville, 2006;Fernandes et al., 2011;Thomas et al., 2013). In primary cell walls, cellulose microfibrils are largely dispersed in a matrix of hemicelluloses and pectins, whereas in secondary walls, microfibrils are typically aggregated into larger bundles, approximately 10 to 20 nm in diameter, which are surrounded by hemicelluloses and lignin and highly aligned with each other (Kennedy et al., 2007;Fernandes et al., 2011). Native cellulose contains a combination of two crystalline allomorphs, I a and I b (Atalla and Vanderhart, 1984), as well as a large fraction of partially disordered chains at the surface of the microfibril and at noncrystalline segments of the microfibril that separate crystallites (Thomas et al., 2013). The structure of cellulose is important because of its fundamental role in plant mechanics, growth, and defense (Cosgrove, 2005) as well as in recalcitrance to enzymatic and chemical conversion to biofuel use (Pauly and Keegstra, 2008).Cellulose in plant cell walls is hierarchically organized, spanning length scales from 10 29 to 10 22 m. At the nanometer...

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Quantification of crystalline cellulose in lignocellulosic biomass using sum frequency generation (SFG) vibration spectroscopy and comparison with other analytical methods

Cited by 75 publications

References 53 publications

Cellulose Synthesis and Its Regulation

Cellulose Synthesis and Its Regulation

Polarization-Sensitive Sum-Frequency Generation Microscopy of Collagen Fibers

Monitoring Meso-Scale Ordering of Cellulose in Intact Plant Cell Walls Using Sum Frequency Generation Spectroscopy

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