About the structure of cellulose: debating the Lindman hypothesis

Glasser, Wolfgang G.; Atalla, Rajai H.; Blackwell, John; Brown, R. Malcolm; Burchard, Walther; French, Alfred D.; Klemm, Dieter; Nishiyama, Yoshiharu

doi:10.1007/s10570-012-9691-7

Cited by 243 publications

(179 citation statements)

References 28 publications

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“…25 In order to stimulate discussion he invited a number of leading researchers in the field to critically examine our views. 26 Unsurprisingly it was found that our views were far from novel or original but that similar findings could be seen in earlier publications. [27][28][29][30] However, such contributions had essentially drowned in a flood of publications identifying hydrogen bonding as the main reason for the insolubility of cellulose in water.…”

Section: Purposesupporting

confidence: 84%

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The relevance of structural features of cellulose and its interactions to dissolution, regeneration, gelation and plasticization phenomena

Lindman

Medronho

Alves

et al. 2017

Phys. Chem. Chem. Phys.

187

109

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aCellulose is the most abundant polymer and a very important renewable resource. Since cellulose cannot be shaped by melting, a major route for its use for novel materials, new chemical compounds and renewable energy must go via the solution state. Investigations during several decades have led to the identification of several solvents of notably different character. The mechanisms of dissolution in terms of intermolecular interactions have been discussed from early work but, even on fundamental aspects, conflicting and opposite views appear. In view of this, strategies for developing new solvent systems for various applications have remained obscure. There is for example a strong need for using forest products for higher value materials and for environmental and cost reasons to use water-based solvents. Several new water-based solvents have been developed recently but there is no consensus regarding the underlying mechanisms. Here we wish to address the most important mechanisms described in the literature and confront them with experimental observations. A broadened view is helpful for improving the current picture and thus cellulose derivatives and phenomena such as fiber dissolution, swelling, regeneration, plasticization and dispersion are considered. In addition to the matter of hydrogen bonding versus hydrophobic interactions, the role of ionization as well as some applications of new knowledge gained are highlighted.

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Section: Purposesupporting

confidence: 84%

“…46 -Cellulose biosynthesis is affected by the presence of hydrophobic substances. 26,47,48 -Ionic liquids are good solvents for cellulose. 49,50 Since these are strongly amphiphilic (and can be characterized as weak surfactants) they fit well into the picture of hydrophobic interactions.…”

mentioning

confidence: 99%

The relevance of structural features of cellulose and its interactions to dissolution, regeneration, gelation and plasticization phenomena

Lindman

Medronho

Alves

et al. 2017

Phys. Chem. Chem. Phys.

187

109

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“…For functional groups on cations such as alkyl-, allyl-, acid-, and ether-, the order of α value was , and Cl -had stronger electron-donating ability, and were easier to break the hydrogen bonds in cellulose to achieve higher solubility, which was consistent with the previous studies (Fukaya et al 2008;Glasser et al 2012).…”

Section: Effect Of Solvent Parameterssupporting

confidence: 88%

Synthesis and Properties of Non-Aromatic Ionic Liquids and their Role in Cellulose Dissolution

Liu¹,

Chen²,

Ren³

et al. 2017

BioResources

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The dissolution of cellulose is an important pretreatment method required for some of its catalytic conversion processes. Morpholinium-based ionic liquids (ILs) are challenging solvent choices available for "greener" and "cheaper" dissolution of cellulose. In this study, morpholinium-based ILs were prepared, and their influencing factors were experimentally investigated. The unique bipolar chemical structure derived from oxygen (electron-rich center) and nitrogen (electron-poor center) considerably enhanced the Hammett acidity function (H0) of task-ILs. N-Methyl-N-allylmorpholinium acetate IL showed the highest H0 (2.324) and polarizability power (1.096). The anion of ILs determined the hydrogen bond basicity (β). The acetate anion contributed to β (0.88) values. As to fluid properties, the morpholinium-based ILs exhibited much lower viscosity. The properties of ILs improved the dissolution efficiency. The cellulose was directly dissolved in morpholinium-based Ils, and no other derivatives were formed. The cations and the anions of ILs studied reacted with oxygen and hydrogen atoms on the hydroxyl groups of cellulose, respectively.

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“…Over decades the hydrogen bonds network in cellulose has been claimed as the reason of the crystalline structure of cellulose and the limitations in cellulose dissolution (Bodvik et al 2010;Zhang et al 2002), while the amphiphilic nature of cellulose has probably been underestimated (Medronho et al 2012. Thus, when developing efficient solvents for cellulose dissolution, not only the intermolecular hydrogen bonds need to be overcome, but also the hydrophobic chain interactions have to be minimized (Glasser et al 2012;Medronho et al 2012).…”

Section: Introductionmentioning

confidence: 99%

Spherical nanocomposite particles prepared from mixed cellulose–chitosan solutions

et al. 2016

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Novel cellulose-chitosan nanocomposite particles with spherical shape were successfully prepared via mixing of aqueous biopolymer solutions in three different ways. Macroparticles with diameters in the millimeter range were produced by dripping cellulose dissolved in cold LiOH/urea into acidic chitosan solutions, inducing instant co-regeneration of the biopolymers. Two types of microspheres, chemically crosslinked and non-crosslinked, were prepared by first mixing cellulose and chitosan solutions obtained from freeze thawing in LiOH/KOH/urea. Thereafter epichlorohydrin was applied as crosslinking agent for one of the samples, followed by water-inoil (W/O) emulsification, heat induced sol-gel transition, solvent exchange, washing and freeze-drying. Characterization by X-ray photoelectron spectroscopy, total elemental analysis, and Fourier transform infrared spectroscopy confirmed the prepared particles as being true cellulose-chitosan nanocomposites with different distribution of chitosan from the surface to the core of the particles depending on the preparation method. Field emission scanning electron microscopy and laser diffraction was performed to study the morphology and size distribution of the prepared particles. The morphology was found to vary due to different preparation routes, revealing a core shell structure for macroparticles prepared by dripping, and homogenous nanoporous structure for the microspheres. The non-crosslinked microparticles exhibited a somewhat denser structure than the crosslinked ones, which indicated that crosslinking restricts packing of the chains before and under regeneration. From the obtained volume-weighted size distributions it was found that the crosslinked microspheres had the highest median diameter. The results demonstrate that not only the mixing ratio and distribution of the two biopolymers, but also the morphology and nanocomposite particle diameters are tunable by choosing between the different routes of preparation.

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About the structure of cellulose: debating the Lindman hypothesis

Cited by 243 publications

References 28 publications

The relevance of structural features of cellulose and its interactions to dissolution, regeneration, gelation and plasticization phenomena

The relevance of structural features of cellulose and its interactions to dissolution, regeneration, gelation and plasticization phenomena

Synthesis and Properties of Non-Aromatic Ionic Liquids and their Role in Cellulose Dissolution

Spherical nanocomposite particles prepared from mixed cellulose–chitosan solutions

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