Rationalizing cellulose (in)solubility: reviewing basic physicochemical aspects and role of hydrophobic interactions

Medronho, Bruno; Romano, Anabela; Miguel, Maria G.; Stigsson, Lars; Lindman, Björn

doi:10.1007/s10570-011-9644-6

Cited by 482 publications

(323 citation statements)

References 28 publications

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“…A naive analogy to the acetate binding observed here would suggest that the mechanism of charging in aqueous TBAH is binding of OH À ions. However, in light of the lack of frustration in aqueous systems (Medronho et al 2012), this appears unlikely. An alternative explanation for the presence of charge on the cellulose chains is provided by the recent observation that cellulose is deprotonated in aqueous alkali (Bialik et al 2016), as anticipated by Lindman et al (Medronho and Lindman 2014;Alves et al 2015).…”

Section: Discussionmentioning

confidence: 99%

On the dissolution of cellulose in tetrabutylammonium acetate/dimethyl sulfoxide: a frustrated solvent

Idström¹,

Gentile

Gubitosi

et al. 2017

Cellulose

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We have found that the dissolution of cellulose in the binary mixed solvent tetrabutylammonium acetate/dimethyl sulfoxide follows a previously overlooked near-stoichiometric relationship such that one dissolved acetate ion is able to dissolve an amount of cellulose corresponding to about one glucose residue. The structure and dynamics of the resulting cellulose solutions were investigated using small-angle X-ray scattering (SAXS) and nuclear magnetic resonance techniques as well as molecular dynamics simulation. This yielded a detailed picture of the dissolution mechanism in which acetate ions form hydrogen bonds to cellulose and causes a diffuse solvation sheath of bulky tetrabutylammonium counterions to form. In turn, this leads to a steric repulsion that helps to keep the cellulose chains apart. Structural similarities to previously investigated cellulose solutions in aqueous tetrabutylammonium hydroxide were revealed by SAXS measurement. To what extent this corresponds to similarities in dissolution mechanism is discussed.

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Section: Discussionmentioning

confidence: 99%

On the dissolution of cellulose in tetrabutylammonium acetate/dimethyl sulfoxide: a frustrated solvent

Idström¹,

Gentile

Gubitosi

et al. 2017

Cellulose

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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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“…Despite the established dominance of the hydrophilic surfaces of cellulose, the amphiphilic character of cellulose, which has been underestimated in the past, is attracting more and more attention (Medronho et al 2012). As it is believed that in some cases, it is the occurrence of minor hydrophobic surfaces that play a determinant role in the reactivity of cellulose.…”

Section: Introductionmentioning

confidence: 99%

Modelling of Congo red adsorption on the hydrophobic surface of cellulose using molecular dynamics

Mazeau

Wyszomirski

2012

Cellulose

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This study describes the interaction between crystalline cellulose and the direct dye Congo red (CR) using molecular dynamics simulations. A model of a microfibril corner of cellulose Ib, exposing one hydrophobic (1 0 0) and the two hydrophilic (1 1 0) and (1 -1 0) surfaces was built. The energetic and geometric features of the dye adsorption were investigated at different temperatures following different initial positions of the CR. The relative positions and orientations of the CR with respect to the cellulose surface were unambiguously characterized using three translation (shift, slide, and rise) and three rotation (roll, tilt, and twist) parameters. Changes of twist and roll parameters showed that there was a tendency for the once adsorbed dye molecules, to become more planar and parallel to the cellulose surface. Several stable adsorption sites, translated laterally with respect to one another were obtained and adsorbed CR molecules were laid with their long axis either parallel or inclined by 50°with respect to the cellulose chain axis. Both vacuum and explicit water environments were considered. In this latter case, there was an increase in the energy of interaction between CR and cellulose and the adsorbed dye molecule behaved more rigidly than in vacuum case.

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Rationalizing cellulose (in)solubility: reviewing basic physicochemical aspects and role of hydrophobic interactions

Cited by 482 publications

References 28 publications

On the dissolution of cellulose in tetrabutylammonium acetate/dimethyl sulfoxide: a frustrated solvent

On the dissolution of cellulose in tetrabutylammonium acetate/dimethyl sulfoxide: a frustrated solvent

Spherical nanocomposite particles prepared from mixed cellulose–chitosan solutions

Modelling of Congo red adsorption on the hydrophobic surface of cellulose using molecular dynamics

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