Solution-State One- and Two-Dimensional NMR Spectroscopy of High-Molecular-Weight Cellulose

Ashley J. Holding; Valtteri Mäkelä; Lasse Tolonen; Herbert Sixta; Ilkka Kilpeläinen; Alistair W.T. King

doi:10.1002/cssc.201501511

Solution-State One- and Two-Dimensional NMR Spectroscopy of High-Molecular-Weight Cellulose

Ashley J. Holding, Valtteri Mäkelä, Lasse Tolonen, Herbert Sixta, Ilkka Kilpeläinen, Alistair W.T. King

Not published at VTT

Research output: Contribution to journal › Article › Scientific › peer-review

22 Citations (Scopus)

Abstract

High-molecular-weight celluloses (which even include bacterial cellulose) can be dissolved fully in methyltrioctylphosphonium acetate/[D₆]DMSO solutions to allow the measurement of resonance-overlap-free 1 D and 2 D NMR spectra. This is achieved by a simple and non-destructive dissolution method, without solvent suppression, pre-treatment or deuteration of the ionic component. We studied a range of cellulose samples by using various NMR experiments to make an a priori assignment of the cellulose resonances. Chain-end resonances are also visible in the ¹H NMR spectrum. This allows the rough determination of the degree of polymerisation (DP) of a sample for low-DP celluloses by the integration of non-reducing chain ends C1 versus polymeric cellobiose C1. Low-DP celluloses show a good agreement with the gel-permeation chromatography (GPC) values, but high-DP pulps show more deviation. For high-purity pulps (pre-hydrolysis kraft and sulfite), residual xyloses and mannoses can also be identified from the ¹H-¹³C heteronuclear single-quantum coherence (HSQC) spectra. Resonances are thus assigned for the common polymeric polysaccharides found in chemical pulps.

Original language	English
Pages (from-to)	880-892
Number of pages	13
Journal	ChemSusChem
Volume	9
Issue number	8
DOIs	https://doi.org/10.1002/cssc.201501511
Publication status	Published - 21 Apr 2016
MoE publication type	A1 Journal article-refereed

Keywords

biomass
carbohydrates
ionic liquids
nmr spectroscopy
polymerization

Access to Document

10.1002/cssc.201501511

Cite this

@article{e9da326cc2e14d88947486cccc1d4706,

title = "Solution-State One- and Two-Dimensional NMR Spectroscopy of High-Molecular-Weight Cellulose",

abstract = "High-molecular-weight celluloses (which even include bacterial cellulose) can be dissolved fully in methyltrioctylphosphonium acetate/[D6]DMSO solutions to allow the measurement of resonance-overlap-free 1 D and 2 D NMR spectra. This is achieved by a simple and non-destructive dissolution method, without solvent suppression, pre-treatment or deuteration of the ionic component. We studied a range of cellulose samples by using various NMR experiments to make an a priori assignment of the cellulose resonances. Chain-end resonances are also visible in the 1H NMR spectrum. This allows the rough determination of the degree of polymerisation (DP) of a sample for low-DP celluloses by the integration of non-reducing chain ends C1 versus polymeric cellobiose C1. Low-DP celluloses show a good agreement with the gel-permeation chromatography (GPC) values, but high-DP pulps show more deviation. For high-purity pulps (pre-hydrolysis kraft and sulfite), residual xyloses and mannoses can also be identified from the 1H-13C heteronuclear single-quantum coherence (HSQC) spectra. Resonances are thus assigned for the common polymeric polysaccharides found in chemical pulps.",

keywords = "biomass, carbohydrates, ionic liquids, nmr spectroscopy, polymerization",

author = "Holding, {Ashley J.} and Valtteri M{\"a}kel{\"a} and Lasse Tolonen and Herbert Sixta and Ilkka Kilpel{\"a}inen and King, {Alistair W.T.}",

note = "Funding Information: We would like to acknowledge CLIC Innovation for funding under the Advanced Cellulose to Novel Products (ACel) program. We would also like to thank Shirin Asaadi for the cotton samples, Stefan Willf?r for the spruce GGM samples and Agnes Stepan for the glucuronoxylan samples. Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2016",

month = apr,

day = "21",

doi = "10.1002/cssc.201501511",

language = "English",

volume = "9",

pages = "880--892",

journal = "ChemSusChem",

issn = "1864-5631",

publisher = "Wiley-VCH Verlag",

number = "8",

}

TY - JOUR

T1 - Solution-State One- and Two-Dimensional NMR Spectroscopy of High-Molecular-Weight Cellulose

AU - Holding, Ashley J.

AU - Mäkelä, Valtteri

AU - Tolonen, Lasse

AU - Sixta, Herbert

AU - Kilpeläinen, Ilkka

AU - King, Alistair W.T.

N1 - Funding Information: We would like to acknowledge CLIC Innovation for funding under the Advanced Cellulose to Novel Products (ACel) program. We would also like to thank Shirin Asaadi for the cotton samples, Stefan Willf?r for the spruce GGM samples and Agnes Stepan for the glucuronoxylan samples. Publisher Copyright: © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

PY - 2016/4/21

Y1 - 2016/4/21

N2 - High-molecular-weight celluloses (which even include bacterial cellulose) can be dissolved fully in methyltrioctylphosphonium acetate/[D6]DMSO solutions to allow the measurement of resonance-overlap-free 1 D and 2 D NMR spectra. This is achieved by a simple and non-destructive dissolution method, without solvent suppression, pre-treatment or deuteration of the ionic component. We studied a range of cellulose samples by using various NMR experiments to make an a priori assignment of the cellulose resonances. Chain-end resonances are also visible in the 1H NMR spectrum. This allows the rough determination of the degree of polymerisation (DP) of a sample for low-DP celluloses by the integration of non-reducing chain ends C1 versus polymeric cellobiose C1. Low-DP celluloses show a good agreement with the gel-permeation chromatography (GPC) values, but high-DP pulps show more deviation. For high-purity pulps (pre-hydrolysis kraft and sulfite), residual xyloses and mannoses can also be identified from the 1H-13C heteronuclear single-quantum coherence (HSQC) spectra. Resonances are thus assigned for the common polymeric polysaccharides found in chemical pulps.

AB - High-molecular-weight celluloses (which even include bacterial cellulose) can be dissolved fully in methyltrioctylphosphonium acetate/[D6]DMSO solutions to allow the measurement of resonance-overlap-free 1 D and 2 D NMR spectra. This is achieved by a simple and non-destructive dissolution method, without solvent suppression, pre-treatment or deuteration of the ionic component. We studied a range of cellulose samples by using various NMR experiments to make an a priori assignment of the cellulose resonances. Chain-end resonances are also visible in the 1H NMR spectrum. This allows the rough determination of the degree of polymerisation (DP) of a sample for low-DP celluloses by the integration of non-reducing chain ends C1 versus polymeric cellobiose C1. Low-DP celluloses show a good agreement with the gel-permeation chromatography (GPC) values, but high-DP pulps show more deviation. For high-purity pulps (pre-hydrolysis kraft and sulfite), residual xyloses and mannoses can also be identified from the 1H-13C heteronuclear single-quantum coherence (HSQC) spectra. Resonances are thus assigned for the common polymeric polysaccharides found in chemical pulps.

KW - biomass

KW - carbohydrates

KW - ionic liquids

KW - nmr spectroscopy

KW - polymerization

UR - http://www.scopus.com/inward/record.url?scp=84979465606&partnerID=8YFLogxK

U2 - 10.1002/cssc.201501511

DO - 10.1002/cssc.201501511

M3 - Article

C2 - 27010664

AN - SCOPUS:84979465606

SN - 1864-5631

VL - 9

SP - 880

EP - 892

JO - ChemSusChem

JF - ChemSusChem

IS - 8

ER -

Solution-State One- and Two-Dimensional NMR Spectroscopy of High-Molecular-Weight Cellulose

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this