Liquid-state NMR analysis of nanocelluloses

Alistair William Thomas King, Arto Valtteri Mäkelä, Stephanie Kedzior, Tiina Marjukka Laaksonen, Gabriel Julian Partl, Sami Mikael Heikkinen, Harri Tapani Koskela, Harri August Heikkinen, Ashley Holding, Emily Cranston, Ilkka Antero Kilpeläinen

Research output: Contribution to journalArticleScientificpeer-review

Abstract

Recent developments in ionic liquid electrolytes for cellulose or biomass dissolution has also allowed for high-resolution 1H and 13C NMR on very high molecular weight cellulose. This permits the development of advanced liquid-state quantitative NMR methods for characterization of unsubstituted and low degree of substitution celluloses, for example, surface-modified nanocelluloses, which are insoluble in all molecular solvents. As such, we present the use of the tetrabutylphosphonium acetate ([P4444][OAc]):DMSO-d6 electrolyte in the 1D and 2D NMR characterization of poly(methyl methacrylate) (PMMA)-grafted cellulose nanocrystals (CNCs). PMMA-g-CNCs was chosen as a difficult model to study, to illustrate the potential of the technique. The chemical shift range of [P4444][OAc] is completely upfield of the cellulose backbone signals, avoiding signal overlap. In addition, application of diffusion-editing for 1H and HSQC was shown to be effective in the discrimination between PMMA polymer graft resonances and those from low molecular weight components arising from the solvent system. The bulk ratio of methyl methacrylate monomer to anhydroglucose unit was determined using a combination of HSQC and quantitative 13C NMR. After detachment and recovery of the PMMA grafts, through methanolysis, DOSY NMR was used to determine the average self-diffusion coefficient and, hence, molecular weight of the grafts compared to self-diffusion coefficients for PMMA GPC standards. This finally led to a calculation of both graft length and graft density using liquid-state NMR techniques. In addition, it was possible to discriminate between triads and tetrads, associated with PMMA tacticity, of the PMMA still attached to the CNCs (before methanolysis). CNC reducing end and sulfate half ester resonances, from sulfuric acid hydrolysis, were also assignable. Furthermore, other biopolymers, such as hemicelluloses and proteins (silk and wool), were found to be soluble in the electrolyte media, allowing for wider application of this method beyond just cellulose analytics.
Original languageEnglish
JournalBiomacromolecules
Volume19
Issue number7
Pages (from-to)2708–2720
Number of pages13
ISSN1525-7797
DOIs
Publication statusPublished - Jul 2018
MoE publication typeA1 Journal article-refereed

Fields of Science

  • 116 Chemical sciences
  • 1182 Biochemistry, cell and molecular biology
  • TRANSFER RADICAL POLYMERIZATION
  • CELLULOSE NANOCRYSTAL SUSPENSIONS
  • CORRELATION SPECTRA
  • IONIC LIQUIDS
  • PICKERING EMULSIONS
  • SPECTROSCOPY
  • FIBERS
  • ATRP
  • MICROFIBRILS
  • COMPOSITES

Cite this

King, Alistair William Thomas ; Mäkelä, Arto Valtteri ; Kedzior, Stephanie ; Laaksonen, Tiina Marjukka ; Partl, Gabriel Julian ; Heikkinen, Sami Mikael ; Koskela, Harri Tapani ; Heikkinen, Harri August ; Holding, Ashley ; Cranston, Emily ; Kilpeläinen, Ilkka Antero. / Liquid-state NMR analysis of nanocelluloses. In: Biomacromolecules. 2018 ; Vol. 19, No. 7. pp. 2708–2720.
@article{e37d4ae02a4c445d9fb79b59c535c8c9,
title = "Liquid-state NMR analysis of nanocelluloses",
abstract = "Recent developments in ionic liquid electrolytes for cellulose or biomass dissolution has also allowed for high-resolution 1H and 13C NMR on very high molecular weight cellulose. This permits the development of advanced liquid-state quantitative NMR methods for characterization of unsubstituted and low degree of substitution celluloses, for example, surface-modified nanocelluloses, which are insoluble in all molecular solvents. As such, we present the use of the tetrabutylphosphonium acetate ([P4444][OAc]):DMSO-d6 electrolyte in the 1D and 2D NMR characterization of poly(methyl methacrylate) (PMMA)-grafted cellulose nanocrystals (CNCs). PMMA-g-CNCs was chosen as a difficult model to study, to illustrate the potential of the technique. The chemical shift range of [P4444][OAc] is completely upfield of the cellulose backbone signals, avoiding signal overlap. In addition, application of diffusion-editing for 1H and HSQC was shown to be effective in the discrimination between PMMA polymer graft resonances and those from low molecular weight components arising from the solvent system. The bulk ratio of methyl methacrylate monomer to anhydroglucose unit was determined using a combination of HSQC and quantitative 13C NMR. After detachment and recovery of the PMMA grafts, through methanolysis, DOSY NMR was used to determine the average self-diffusion coefficient and, hence, molecular weight of the grafts compared to self-diffusion coefficients for PMMA GPC standards. This finally led to a calculation of both graft length and graft density using liquid-state NMR techniques. In addition, it was possible to discriminate between triads and tetrads, associated with PMMA tacticity, of the PMMA still attached to the CNCs (before methanolysis). CNC reducing end and sulfate half ester resonances, from sulfuric acid hydrolysis, were also assignable. Furthermore, other biopolymers, such as hemicelluloses and proteins (silk and wool), were found to be soluble in the electrolyte media, allowing for wider application of this method beyond just cellulose analytics.",
keywords = "116 Chemical sciences, 1182 Biochemistry, cell and molecular biology, TRANSFER RADICAL POLYMERIZATION, CELLULOSE NANOCRYSTAL SUSPENSIONS, CORRELATION SPECTRA, IONIC LIQUIDS, PICKERING EMULSIONS, SPECTROSCOPY, FIBERS, ATRP, MICROFIBRILS, COMPOSITES",
author = "King, {Alistair William Thomas} and M{\"a}kel{\"a}, {Arto Valtteri} and Stephanie Kedzior and Laaksonen, {Tiina Marjukka} and Partl, {Gabriel Julian} and Heikkinen, {Sami Mikael} and Koskela, {Harri Tapani} and Heikkinen, {Harri August} and Ashley Holding and Emily Cranston and Kilpel{\"a}inen, {Ilkka Antero}",
year = "2018",
month = "7",
doi = "10.1021/acs.biomac.8b00295",
language = "English",
volume = "19",
pages = "2708–2720",
journal = "Biomacromolecules",
issn = "1525-7797",
publisher = "American Chemical Society",
number = "7",

}

King, AWT, Mäkelä, AV, Kedzior, S, Laaksonen, TM, Partl, GJ, Heikkinen, SM, Koskela, HT, Heikkinen, HA, Holding, A, Cranston, E & Kilpeläinen, IA 2018, 'Liquid-state NMR analysis of nanocelluloses' Biomacromolecules, vol. 19, no. 7, pp. 2708–2720. https://doi.org/10.1021/acs.biomac.8b00295

Liquid-state NMR analysis of nanocelluloses. / King, Alistair William Thomas; Mäkelä, Arto Valtteri; Kedzior, Stephanie; Laaksonen, Tiina Marjukka; Partl, Gabriel Julian; Heikkinen, Sami Mikael; Koskela, Harri Tapani; Heikkinen, Harri August; Holding, Ashley; Cranston, Emily; Kilpeläinen, Ilkka Antero.

In: Biomacromolecules, Vol. 19, No. 7, 07.2018, p. 2708–2720.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Liquid-state NMR analysis of nanocelluloses

AU - King, Alistair William Thomas

AU - Mäkelä, Arto Valtteri

AU - Kedzior, Stephanie

AU - Laaksonen, Tiina Marjukka

AU - Partl, Gabriel Julian

AU - Heikkinen, Sami Mikael

AU - Koskela, Harri Tapani

AU - Heikkinen, Harri August

AU - Holding, Ashley

AU - Cranston, Emily

AU - Kilpeläinen, Ilkka Antero

PY - 2018/7

Y1 - 2018/7

N2 - Recent developments in ionic liquid electrolytes for cellulose or biomass dissolution has also allowed for high-resolution 1H and 13C NMR on very high molecular weight cellulose. This permits the development of advanced liquid-state quantitative NMR methods for characterization of unsubstituted and low degree of substitution celluloses, for example, surface-modified nanocelluloses, which are insoluble in all molecular solvents. As such, we present the use of the tetrabutylphosphonium acetate ([P4444][OAc]):DMSO-d6 electrolyte in the 1D and 2D NMR characterization of poly(methyl methacrylate) (PMMA)-grafted cellulose nanocrystals (CNCs). PMMA-g-CNCs was chosen as a difficult model to study, to illustrate the potential of the technique. The chemical shift range of [P4444][OAc] is completely upfield of the cellulose backbone signals, avoiding signal overlap. In addition, application of diffusion-editing for 1H and HSQC was shown to be effective in the discrimination between PMMA polymer graft resonances and those from low molecular weight components arising from the solvent system. The bulk ratio of methyl methacrylate monomer to anhydroglucose unit was determined using a combination of HSQC and quantitative 13C NMR. After detachment and recovery of the PMMA grafts, through methanolysis, DOSY NMR was used to determine the average self-diffusion coefficient and, hence, molecular weight of the grafts compared to self-diffusion coefficients for PMMA GPC standards. This finally led to a calculation of both graft length and graft density using liquid-state NMR techniques. In addition, it was possible to discriminate between triads and tetrads, associated with PMMA tacticity, of the PMMA still attached to the CNCs (before methanolysis). CNC reducing end and sulfate half ester resonances, from sulfuric acid hydrolysis, were also assignable. Furthermore, other biopolymers, such as hemicelluloses and proteins (silk and wool), were found to be soluble in the electrolyte media, allowing for wider application of this method beyond just cellulose analytics.

AB - Recent developments in ionic liquid electrolytes for cellulose or biomass dissolution has also allowed for high-resolution 1H and 13C NMR on very high molecular weight cellulose. This permits the development of advanced liquid-state quantitative NMR methods for characterization of unsubstituted and low degree of substitution celluloses, for example, surface-modified nanocelluloses, which are insoluble in all molecular solvents. As such, we present the use of the tetrabutylphosphonium acetate ([P4444][OAc]):DMSO-d6 electrolyte in the 1D and 2D NMR characterization of poly(methyl methacrylate) (PMMA)-grafted cellulose nanocrystals (CNCs). PMMA-g-CNCs was chosen as a difficult model to study, to illustrate the potential of the technique. The chemical shift range of [P4444][OAc] is completely upfield of the cellulose backbone signals, avoiding signal overlap. In addition, application of diffusion-editing for 1H and HSQC was shown to be effective in the discrimination between PMMA polymer graft resonances and those from low molecular weight components arising from the solvent system. The bulk ratio of methyl methacrylate monomer to anhydroglucose unit was determined using a combination of HSQC and quantitative 13C NMR. After detachment and recovery of the PMMA grafts, through methanolysis, DOSY NMR was used to determine the average self-diffusion coefficient and, hence, molecular weight of the grafts compared to self-diffusion coefficients for PMMA GPC standards. This finally led to a calculation of both graft length and graft density using liquid-state NMR techniques. In addition, it was possible to discriminate between triads and tetrads, associated with PMMA tacticity, of the PMMA still attached to the CNCs (before methanolysis). CNC reducing end and sulfate half ester resonances, from sulfuric acid hydrolysis, were also assignable. Furthermore, other biopolymers, such as hemicelluloses and proteins (silk and wool), were found to be soluble in the electrolyte media, allowing for wider application of this method beyond just cellulose analytics.

KW - 116 Chemical sciences

KW - 1182 Biochemistry, cell and molecular biology

KW - TRANSFER RADICAL POLYMERIZATION

KW - CELLULOSE NANOCRYSTAL SUSPENSIONS

KW - CORRELATION SPECTRA

KW - IONIC LIQUIDS

KW - PICKERING EMULSIONS

KW - SPECTROSCOPY

KW - FIBERS

KW - ATRP

KW - MICROFIBRILS

KW - COMPOSITES

U2 - 10.1021/acs.biomac.8b00295

DO - 10.1021/acs.biomac.8b00295

M3 - Article

VL - 19

SP - 2708

EP - 2720

JO - Biomacromolecules

JF - Biomacromolecules

SN - 1525-7797

IS - 7

ER -

King AWT, Mäkelä AV, Kedzior S, Laaksonen TM, Partl GJ, Heikkinen SM et al. Liquid-state NMR analysis of nanocelluloses. Biomacromolecules. 2018 Jul;19(7):2708–2720. https://doi.org/10.1021/acs.biomac.8b00295