Dependence of cellulose dissolution in quaternary ammonium acetates/DMSO on the molecular structure of the electrolyte: use of solvatochromism, micro-calorimetry, and molecular dynamics simulations

Kostag, Marc; Pires, Paulo A. R.; El Seoud, Omar A.

doi:10.1007/s10570-020-03050-8

Dependence of cellulose dissolution in quaternary ammonium acetates/DMSO on the molecular structure of the electrolyte: use of solvatochromism, micro-calorimetry, and molecular dynamics simulations

Original Research
Published: 25 February 2020

Volume 27, pages 3565–3580, (2020)
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Abstract

We studied the dissolution of microcrystalline cellulose (MCC) at 60 °C in binary mixtures of dimethyl sulfoxide (DMSO) and the following quaternary ammonium acetates (QAAcOs): benzyl-trimethylammonium, N_BzMe3AcO; diallyl-benzyl-methylammonium, N_Al2BzMeAcO, tetra(n-butyl)ammonium (N_Bu4AcO), and tribenzyl-methylammonium, N_Bz3MeAcO (Al, Bu, Bz, Me, AcO refer to allyl, 1-butyl, benzyl, methyl and acetate group, respectively). We observed the following MCC dissolution order (given as wt%): N_Bu4AcO > N_Al2BzMeAcO > N_Bz3MeAcO ≫ N_BzMe3AcO. To explain this result we used the combined data of: (1) solvatochromism to calculate the following binary solvent (b-solvent) descriptors that are important for MCC dissolution: empirical polarity, Lewis acidity, Lewis basicity, dipolarity, polarizability; (2) isothermal titration micro-calorimetry to calculate the enthalpy of interaction (ΔH) of β-cyclodextrin (cellulose model) with QAAcO/DMSO-acetonitrile; (3) molecular dynamics simulations to calculate solvent-induced separation of cellulose chains; average number of hydrogen bonds between acetate ions and cellulose OH-groups, and average composition of the biopolymer solvation layer. We offer the following pieces of evidence to show the importance of hydrogen bonding for the efficiency of cellulose dissolution: the orders of b-solvent basicity and of |ΔH| are parallel to its cellulose dissolution efficiency; the biopolymer solvation layer of efficient b-solvents (e.g., N_Bu4AcO-DMSO) contains more ionic liquid ions and less DMSO molecules than that of N_Bz3MeAcO, leading to pronounced biopolymer chain separation, hence eventual dissolution. Our approach shows the power of the combined use of several techniques to rationalize the requirements for efficient cellulose solvents.

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Abbreviations

AcO:: Acetate
AGU:: Anhydroglucose unit
Al:: Allyl
Ant:: Anthracene
b-solvent:: Binary solvent mixture
Bu:: 1-Butyl
Bz:: Benzyl
Cel-OH:: Hydroxyl group of the AGU
β-CD:: β-Cyclodextrin
DMANF:: 2-(N,N-dimethylamino)-7-nitro-9H-fluorene
DMSO:: Dimethyl sulfoxide
Fe:: [Fe^III(1,10-phenanthroline)₂(CN)₂]ClO₄
H-bonding:: Hydrogen bonding
H-bonds:: Hydrogen bonds
IL:: Ionic liquid
ITC:: Isothermal titration calorimetry
MCC:: Microcrystalline cellulose
MD:: Molecular dynamics
Me:: Methyl
MeCN:: Acetonitrile
MeNI:: 1-Methyl-5-nitroindoline
NI:: 5-Nitroindoline
N_Bu4 :: Tetra(n-butyl)ammonium
N_BzMe3 :: Benzyl-trimethylammonium
N_Al2BzMe :: Diallyl-benzyl-methylammonium (Al-Allyl)
N_Bz3Me :: Tribenzyl-methylammonium
OES:: Organic electrolyte solution (electrolytes/organic solvent mixtures)
QAAcO:: Quaternary ammonium acetate
QAE:: Quaternary ammonium electrolyte
RDF:: Radial distribution function
S:: Solvent
SA :: Solvent Lewis acidity
SB :: Solvent Lewis basicity
SD :: Solvent dipolarity
SP :: Solvent polarizability
WB:: 2,6-Dichloro-4-(2,4,6-triphenyl-pyridinium-1-yl)phenolate
ΔH :: Excess partial molar enthalpy (interaction enthalpy of β-CD with QAAcOs)
χ:: Mole fraction

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Acknowledgments

O. A. El Seoud and M. Kostag thank FAPESP (Fundação de Amparo à Pesquisa do Estado de São Paulo) for financial support and postdoctoral fellowship (Grants 2014/22136-4, 2017/06394-1 and 2016/22869-7, respectively). O. A. El Seoud thanks CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico) for research productivity fellowship (Grant 307022/2014-5). We thank Cezar Guizzo and Nicolas Keppeler for help with Fig. 2 and the references.

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Institute of Chemistry, The University of São Paulo, 748 Prof. Lineu Prestes Av., São Paulo, SP, 05508-000, Brazil
Marc Kostag, Paulo A. R. Pires & Omar A. El Seoud

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Kostag, M., Pires, P.A.R. & El Seoud, O.A. Dependence of cellulose dissolution in quaternary ammonium acetates/DMSO on the molecular structure of the electrolyte: use of solvatochromism, micro-calorimetry, and molecular dynamics simulations. Cellulose 27, 3565–3580 (2020). https://doi.org/10.1007/s10570-020-03050-8

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Received: 16 November 2019
Accepted: 07 February 2020
Published: 25 February 2020
Issue Date: May 2020
DOI: https://doi.org/10.1007/s10570-020-03050-8

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