Sascha Gehrke

Is Carbene Formation Necessary for Dissolving Cellulose in Ionic Liquids

In this work we explored through molecular dynamics simulations how the dissolution of cellulose and its fragments in 1-ethyl-3-methylimidazolium acetate is affected by the inherent accessibility of carbenes in this solvent. We show that-apart from the decomposition reactions-carbenes do not interact strongly with the solute carbohydrates, as the solute-solvent interactions are dominated by the anion. On the other hand, the formation of the carbene is hindered by the hydrogen bond donor hydroxyl groups at the carbohydrate through occupying the anion, and hence disrupting the anion-cation interplay. Comparing the rate of dissolution of a cellulose bundle in the pure IL to that in the presence of carbenes showed that not only the cellulose hinders the carbene formation, but the presence of carbenes also make the dissolution of the cellulose slower. Accordingly, although based on indirect experimental findings one might speculate otherwise, the solubility and carbene formation are merely two independent consequences of the basicity of the ionic liquid anion, and the presence of carbenes is not necessary for breaking up the cellulose into individual chains. Based on these results we can conclude that it is, in principle, possible to design an ionic liquid that is an ideal solvent for this biopolymer, which dissolves, but does not decompose cellulose.

How to Harvest Grotthuss Diffusion in Protic Ionic Liquid Electrolyte Systems

Hydrogen is often regarded as fuel of the future, and there is an increasing demand for the development of anhydrous proton-conducting electrolytes to enable fuel-cell operation at elevated temperatures exceeding 120 °C. Much attention has been directed at protic ionic liquids as promising candidates, but in the search for highly conductive systems the possibility of designing Grotthuss diffusion-enabled protic ionic liquids has been widely overlooked. Herein, the mechanics of proton-transfer mechanism in the equimolar mixture of N-methylimidazole and acetic acid was explored using ab initio molecular dynamics simulations. The ionicity of the system is approximated with good agreement to experiments. This system consists mostly of neutral species but exhibits a high ionic conductivity through Grotthuss-like proton conduction. Chains of acetic-acid molecules and other species participating in the proton-transfer mechanisms resembling Grotthuss diffusion could be directly observed. Furthermore, based on these findings, a series of static quantum chemical calculations was conducted to investigate the effect of substituting the anion and cation with different functional groups. We predict whether a given combination of cation and anion will be a true ionic liquid or a molecular mixture and propose some systems as candidates for Grotthuss diffusion-enabled protic ionic liquids.

Hydrogen Bonding of N-Heterocyclic Carbenes in Solution: Mechanisms of Solvent Reorganization

The hydrogen-bond dynamics of N-heterocyclic carbenes plays a central role in their proton-transfer reactions, and the effects of hydrogen bonding are also often invoked in corresponding organocatalytic applications. In the present study, the structures and lifetimes of hydrogen bonds have been investigated for several carbenes in alcohol-containing solutions by classical molecular dynamics simulations. The basicity of the carbene was found to be of major importance; while the least basic carbenes are often in their free form in the solvent, by increasing the basicity the simulations show increased hydrogen bonding, often even with two alcohol molecules at a time. In the latter structure the single lone pair of the carbene is in interplay with two hydrogen bond donors. The exchange mechanism is different for carbenes with different basicities, with different substituents, and in different solvents, occurring through the free carbene for the least basic compounds, and through the aforementioned doubly-hydrogen-bonded structure in case of the most basic derivatives. Since this process plays a central role also in H/D exchange reactions, we argue that the pK values calculated from the related measurements have a varying physical meaning for the different carbenes. The lifetimes of the hydrogen bonds are apparently also clearly related to the basicity of the carbene, with gradually increasing lifetimes for the most basic compounds.

NMR relaxometric probing of ionic liquid dynamics and diffusion under mesoscopic confinement within bacterial cellulose ionogels

Bacterial cellulose ionogels (BCIGs) represent a new class of material comprising a significant content of entrapped ionic liquid (IL) within a porous network formed from crystalline cellulose microfibrils. BCIGs suggest unique opportunities in separations, optically active materials, solid electrolytes, and drug delivery due to the fact that they can contain as much as 99% of an IL phase by weight, coupled with an inherent flexibility, high optical transparency, and the ability to control ionogel cross-sectional shape and size. To allow for the tailoring of BCIGs for a multitude of applications, it is necessary to better understand the underlying principles of the mesoscopic confinement within these ionogels. Toward this, we present a study of the structural, relaxation, and diffusional properties of the ILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([bmpy][Tf2N]), using 1H and 19F NMR T1 relaxation times, rotational correlation times, and diffusion ordered spectroscopy (DOSY) diffusion coefficients, accompanied by molecular dynamics (MD) simulations. We observed that the cation methyl groups in both ILs were primary points of interaction with the cellulose chains and, while the pore size in cellulose is rather large, [emim]+ diffusion was slowed by ∼2-fold, whereas [Tf2N]- diffusion was unencumbered by incorporation in the ionogel. While MD simulations of [bmpy][Tf2N] confinement at the interface showed a diffusion coefficient decrease roughly 3-fold compared to the bulk liquid, DOSY measurements did not reveal any significant changes in diffusion. This suggests that the [bmpy][Tf2N] alkyl chains dominate diffusion through formation of apolar domains. This is in contrast to [emim][Tf2N] where delocalized charge appears to preclude apolar domain formation, allowing interfacial effects to be manifested at a longer range in [emim][Tf2N].

Ab initio simulations of bond breaking in sulfur crosslinked isoprene oligomer units

Sulfur crosslinked polyisoprene (rubber) is used in important material components for a number of technical tasks (e.g., in tires and sealings). If mechanical stress, like tension or shear, is applied on these material components, the sulfur crosslinks suffer from homolytic bond breaking. In this work, we have simulated the bond breaking mechanism of sulfur crosslinks between polyisoprene chains using Car-Parrinello molecular dynamic simulations and investigated the maximum forces which can be resisted by the crosslinks. Small model systems with crosslinks formed by chains of N = 1 to N = 6 sulfur atoms have been simulated with the slow growth-technique, known from the literature. The maximum force can be thereby determined from the calculated energies as a function of strain (elongation). The stability of the crosslink under strain is quantified in terms of the maximum force that can be resisted by the system before the crosslink breaks. As shown by our simulations, this maximum force decreases with the sulfur crosslink length N in a step like manner. Our findings indicate that in bridges with N = 1, 2, and 3 sulfur atoms predominantly, carbon-sulfur bonds break, while in crosslinks with N > 3, the breaking of a sulfur-sulfur bond is the dominant failure mechanism. The results are explained within a simple chemical bond model, which describes how the delocalization of the electrons in the generated radicals can lower their electronic energy and decrease the activation barriers. It is described which of the double bonds in the isoprene units are involved in the mechanochemistry of crosslinked rubber.