Structures, intermolecular interactions, and chemical hardness of binary water–organic solvents: a molecular dynamics study

Aguilera-Segura, Sonia Milena; Renzo, Francesco Di; Mineva, Tzonka

doi:10.1007/s00894-018-3817-2

Cited by 4 publications

(8 citation statements)

References 85 publications

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“…The study of the interaction of poplar wood and its components with water-ethanol solutions and their vapors confirms that wood is an effective model for the study of the peculiar behavior of composite materials exposed to mixed solvents. Two kinds of non-linearity play a role in the behavior of composite materials exposed to mixed solvents: (i) the colligative properties of ethanol aqueous solutions are themselves not linear with their composition; [37] (ii) moreover, the differential interactions of each component of the solvent with specific components of the composite material creates further non-linearity of the sorption and mechanical properties of the material. Several instances of "hyperswelling" of wood in the ethanolwater system can be observed, namely an effect of mixed solution exceeding the linear combination of the effects observed with individual solvent components.…”

Section: Discussionmentioning

confidence: 99%

“…Solvent accessible surfaces were computed using the double cubic lattice method (DCLM) by using a solvent probe radius of 0.14 nm. Further details of the MD simulations and the description of the tools used for analysis can be found in our previous work on water‐ethanol mixture interactions …”

Section: Methodsmentioning

confidence: 99%

“…Further details of the MD simulations and the description of the tools used for analysis can be found in our previous work on water-ethanol mixture interactions. [37]…”

Section: Methodsmentioning

confidence: 99%

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Synergistic Sorption of Mixed Solvents in Wood Cell Walls: Experimental and Theoretical Approach

Aguilera-Segura

Bossu

Corn

et al. 2019

Macromolecular Symposia

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The behavior of poplar wood and its components in water‐ethanol mixtures is investigated through a coupled experimental and theoretical approach including physico‐chemical and dynamic mechanical analyses and molecular dynamics simulations. Affinity for water‐ethanol vapors, measured by isothermal gravimetric sorption experiments, features a maximum for mixed vapors. The longitudinal viscoelastic behavior of the same wood upon immersion in ethanol‐water solutions, measured by dynamic mechanical analysis, features a minimum in storage modulus and a maximum damping upon immersion in solutions of intermediate composition. Optical microscopy observation of solvent‐saturated samples evidences inter‐ and intra‐cellular disbonding in pure ethanol and ethanol aqueous solutions. Molecular dynamics simulations provide information on interactions of water‐ethanol solutions with models of cellulose microfibers and lignin. The relative solvation of cellulose microfibers by water and ethanol shows a nearly linear variation with the composition of the solution. In contrast, the accessibility of lignin dimers to the solvent presents a maximum at intermediate ethanol concentrations, in correspondence with a conformational transition of the dimer towards an extended conformation. The modelization of the interactions of cellulose and lignin in water‐ethanol solutions indicates a minimum of adhesion of the two components of wood in the presence of solutions with intermediate concentrations.

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Section: Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Synergistic Sorption of Mixed Solvents in Wood Cell Walls: Experimental and Theoretical Approach

Aguilera-Segura

Bossu

Corn

et al. 2019

Macromolecular Symposia

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“…This is most likely because of dipole–dipole interactions between acetonitrile molecules, which displace methyl groups toward the cellulose surface and form O cellulose ···H–CMe bonds. Moreover, the local microheterogeneity of water–acetonitrile mixtures could enhance the water–acetonitrile separation when in contact with the different cellulose surfaces as exemplified in Figure B,C. Ethanol and water, on the contrary, remain less separated, as ethanol–water mixtures are more homogeneous and both components share a similar affinity for a specific oxygen site in cellulose.…”

Section: Resultsmentioning

confidence: 99%

“…The lignin–cellulose interaction energies and their evolution with dynamic simulations demonstrate that the introduction of the organic solvents in water results in a substantial disruption of lignin–cellulose interactions. The addition of the organic phase (ethanol/acetonitrile) predominantly modifies the cellulose solvation shells, resulting in reduced mobility of water molecules because of the longer-lasting cellulose–water H-bonds (in Table S6), concomitant with the longer-lasting water–ethanol and water–acetonitrile H-bonds than the water–water H-bonds in the bulk water . In addition to the effect on the water mobility, the organic phases compete with water for the same cellulose coordination site, which interferes with the lignin adsorption on cellulose.…”

Section: Resultsmentioning

confidence: 99%

Molecular Insight into the Cosolvent Effect on Lignin–Cellulose Adhesion

2020

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Understanding and controlling the physical adsorption of lignin compounds on cellulose pulp is a key parameter for a successful optimization of organosolv processes. The effect of binary organic-aqueous solvents on the coordination of lignin to cellulose was studied with molecular dynamics simulations, considering ethanol and acetonitrile as organic co-solvents in aqueous solutions in comparison to their mono-component counterparts. The structures of the solvation shells around cellulose and lignin, as well as the energetics of the lignin-cellulose adhesion, indicate a more effective disruption of lignin-cellulose binding by binary solvents. The synergic effect between solvent components is explained by their preferential interactions with celluloselignin complexes. In the presence of pure water, long-lasting H-bonds in the lignin-cellulose complex are observed, promoted by the non-favorable interactions of lignin with water. Ethanol and acetonitrile compete with water and lignin for cellulose oxygen binding sites, causing a non-linear decrease of the cellulose-lignin interactions with the amount of the organic component. This effect is modulated by the water exclusion from the cellulose solvation shell by the organic solvent component. The amount and rate of water exclusion depend on the type of organic cosolvent and its concentration.

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The Effect of Electric Fields on the Structure of Water/Acetonitrile Mixtures

Sourpis,

Forero-Martinez,

Schmid

2023

J. Electrochem. Soc.

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We study the effect of external electric fields on the structure of water/acetonitrile mixtures at high acetonitrile content by molecular dynamics simulations. We find that the linear response regime extends up to roughly 0.03 V /nm in these mixtures, then nonlinear behavior sets in. The most pronounced nonlinear effect of electric field is a change of relative orientations of neighboring acetonitrile molecules, from predominantly antiparallel to predominantly parallel. Nevertheless, the hydrogen bond network topology remains remarkably stable and conserves its overall properties in the whole range of considered applied fields up to 0.5 V /nm, which is far beyond the dielectric breakdown limit of pure water.

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Structures, intermolecular interactions, and chemical hardness of binary water–organic solvents: a molecular dynamics study

Cited by 4 publications

References 85 publications

Synergistic Sorption of Mixed Solvents in Wood Cell Walls: Experimental and Theoretical Approach

Synergistic Sorption of Mixed Solvents in Wood Cell Walls: Experimental and Theoretical Approach

Molecular Insight into the Cosolvent Effect on Lignin–Cellulose Adhesion

The Effect of Electric Fields on the Structure of Water/Acetonitrile Mixtures

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