The nanostructural organization of liquid crystals (LC) creates unique opportunities for designing electrolytes with adaptive ion-transport properties. LC additives act as dynamic regulators of ion flow, balancing charge storage and energy release through local stimuli-responsive reorganization. LC functionalization has been shown to reduce self-discharge in supercapacitors, suppress dendrite formation in lithium–metal batteries, and enhance the ionic conductivity via self-assembled structures. However, the fundamental mechanisms behind these benefits remain poorly understood. Here, we investigate LiTFSI-based electrolytes doped with the mesogen 4-cyano-4′-pentylbiphenyl (5CB) using a range of solution- and solid-state NMR techniques. Heteronuclear Overhauser effect spectroscopy confirms molecular-level mixing across a broad LC concentration range. Pulsed-field gradient and electrophoretic NMR reveal composition-dependent trends in ion dynamics. Our findings show that ion mobility is governed not by LC alignment near electrode interfaces but rather by local LC concentration and specific ion–LC interactions. These results emphasize the importance of composition-driven and interfacial control of ion transport in LC-functionalized electrolytes over strategies that rely solely on mesogen alignment.

Directed ion transport is captured by tensor-resolved NMR.

Controlling the dimensionality of ion transport is a powerful strategy for designing high-performance electrolytes, yet direct experimental access to anisotropic ion dynamics at the molecular level remains limited. Here, we apply an orientation-selective NMR methodology to determine temperature-dependent diffusion and electrophoretic mobility tensors of the ionic liquid crystal C 12 mimBF 4 across its isotropic and smectic phases. The results reveal a pronounced reorganization of transport at the isotropic–smectic transition: isotropic, spatially homogeneous motion transforms into anisotropic transport with enhanced in-layer mobility and suppressed cross-layer migration. Despite this redistribution, orientationally averaged transport coefficients remain continuous across the transition, indicating that structural ordering redirects rather than amplifies ion motion. Electrophoretic mobilities show near-quantitative agreement with macroscopic conductivity, while only minor deviations from the Einstein–Smoluchowski relation are observed for the anions, consistent with weak ion–ion correlations. Our findings identify anions as the dominant charge carriers within polar channels and demonstrate how self-assembled structure enforces quasi-two-dimensional ion conduction. The approach provides a general framework for resolving anisotropic transport in soft matter electrolytes.

Although macroscopic ionic transport tensors, such as conductivity, are readily measured, accessing ion-specific, direction-dependent transport at the molecular level remains experimentally challenging. Here, we introduce a frequency-selective NMR methodology that enables direct measurement of diffusion and electrophoretic mobility tensors in ordered electrolytes. The approach exploits the orientational encoding inherent in anisotropic powder spectra as an angular filter and employs soft radiofrequency pulses to isolate narrow subsets of molecular orientations. This filtering converts conventional PGSE-NMR and electrophoretic NMR experiments into tensor-resolved measurements. Broadly applicable to systems with direction-dependent spin interactions, the method provides access to the principal components of electrophoretic mobility and diffusion tensors within a unified experimental framework. Demonstrated on a smectic ionic liquid crystal as a model ordered electrolyte, the technique yields the first direct experimental determination of anisotropic electrophoretic mobility in such materials. The methodology establishes a general experimentally accessible route to tensor-resolved transport measurements in complex anisotropic conductors relevant to electrochemical applications.

Even at very low concentrations, the rheology of dispersions of charged semi-flexible nanofibers differs from the rheology of the pure liquid, given the fiber charge, morphology and interactions. At the nanoscale, the thermal motion of fibers is driven by the collective motion of the solvent molecules, but to what extent does the fiber presence and motion affect the self-diffusion of the liquid molecules? By studying the self-diffusion of water in dilute nanofiber dispersions using experiments and simulations, we can show that the interplay of fiber charge and motion on water mobility is more significant than the effect of the excluded volume caused by the charged particles.

Green chemical modification of cellulose presents a unique chemical challenge, especially from the vantage point of sustainable development that is favored by the use of wood fibers, heterogeneous conditions, and reactants and solvents of biobased relevance. However, heterogeneous conditions imply that cellulose is a supramolecular assembly whose composition and build-up depend on the initial source and pretreatments. Also, understanding reaction outcomes is accompanied by inherently challenging characterization. The key question is how we should design our reaction systems to achieve customizable and green functionalization of cellulose under heterogeneous conditions. To explore this, we selected never-dried high-content cellulose fibers (>96 % cellulose) as the substrate for the modification with three relevant biobased reactants (succinic, maleic, and crotonic anhydride), with BBIL-AcO as a biobased reactivity promoter. The reactions were performed under either high fiber swelling (basic) or low fiber swelling (acidic) heterogeneous conditions, and the outcome was analyzed in detail. The results unravel clear design strategies for controlling the reaction outcome during the green heterogeneous functionalization of cellulose and present clear synthetic strategies for using cellulose as the key substrate in the next generation of fully biobased and green materials.

Biopolymers, especially cellulose, are vital to transitioning to a circular economy and reducing our reliance on fossil fuels. However, for many applications a high degree of cellulose hydroxyl modification is necessary. The challenge is that the chemical features of the hydroxyls of cellulose and water are similar. Therefore, chemical modification of cellulose is often explored under non-aqueous conditions with systems that result in high hydroxyl accessibility and reduce cellulose aggregation. Unfortunately, these systems depend on hazardous and complex solvents from fossil resources, which diverge from the initial sustainability objectives. To address this, we developed three new betaine-based ionic liquids that are fully bio-based, scalable, and green. We found that a specific ionic liquid had the perfect chemical features for the chemical activation of cellulose without disturbing its crystalline ordering. The high activation in heterogeneous conditions was exemplified by reacting cellulose with succinic anhydride, resulting in more than 30 % conversion of all hydroxyls on cellulose. Overall, this work opens new perspectives for the derivatization of cellulosic materials while simultaneously “keeping it green”.

Binary mixtures of ethanol and phospholipids DOPC and DOPE have been investigated in a composition range relevant for topical drug delivery applications. This was done using a combined computer simulation and experimental approach where molecular dynamics simulations of ethanol-lipid mixtures with different compositions were performed. Several key properties including diffusion coefficients, longitudinal relaxation times, and shear viscosity were computed. In addition, diffusion coefficients, viscosities and NMR longitudinal relaxation times were measured experimentally for comparison and in order to validate the results from simulation. Diffusion coefficients and relaxation times obtained from simulations are in good agreement with results from NMR and computed viscosities are in reasonable agreement with viscometry experiments indicating that the simulations provide a realistic description of the ethanol-phospholipid mixtures. Structural changes in the simulated systems were investigated using an analysis based on radial distribution functions. This showed that the structure of ethanol-DOPC mixtures remains essentially unchanged in the investigated concentration range while ethanol-DOPE mixtures undergo structural rearrangements with the tendency for forming small aggregates on the 100 ns time scale consisting of less than 10 lipids. Although our simulations and experiments indicate that no larger aggregates form, they also show that DOPE has stronger aggregation tendency than DOPC. This highlights the importance of the character of the lipid headgroup for lipid aggregation in ethanol and gives new insights into phase equilibrium, dynamics and rheology that could be valuable for the development of advanced topical drug delivery formulations.

Cellulose nanofibril (CNF) materials are candidates for the sustainable development of high mechanical performance nanomaterials. Due to inherent hydrophilicity and limited functionality range, most applications require chemical modification of CNF. However, targeted transformations directly on CNF are cumbersome due to the propensity of CNF to aggregate in non-aqueous solvents at high concentrations, complicating the choice of suitable reagents and requiring tedious separations of the final product. This work addresses this challenge by developing a general, entirely water-based, and experimentally simple methodology for functionalizing CNF, providing aliphatic, allylic, propargylic, azobenzylic, and substituted benzylic functional groups. The first step is NaIO4 oxidation to dialdehyde-CNF in the wet cake state, followed by oxime ligation with O-substituted hydroxylamines. The increased hydrolytic stability of oximes removes the need for reductive stabilization as often required for the analogous imines where aldehyde groups react with amines in water. Overall, the process provides a tailored degree of nanofibril functionalization (2-4.5 mmol/g) with the possible reversible detachment of the functionality under mildly acidic conditions, resulting in the reformation of dialdehyde CNF. The modified CNF materials were assessed for potential applications in green electronics and triboelectric nanogenerators. Water is a standing challenge in the chemical modification of cellulose nanofibrils. Here, authors employ oxime-ligation to solve this by direct covalent chemistry on dialdehyde-CNF in water and assess the material for potential applications in green electronics and triboelectric nanogenerators.

The hydrogen-bonding interaction is studied in imidazolium-based mesogenic ionic liquids in their isotropic, smectic, and solid phases and in a nanoconfined state by proton solid-state nuclear magnetic resonance (NMR). In the smectic phase, the more basic anions form stronger hydrogen bonds. A small decrease of H-bonding in the mesophase with respect to that in the isotropic phase is associated with the presence of a layered assembly with high orientational order and limited conformational freedom. Hydrogen bond strength is not sensitive to the cation structural modification as long as the aprotic nature of the material is preserved. The strong cation-anion hydrogen bonding observed in the smectic phases provides direct support for the presence of ionic sublayers which form in ionic liquid crystals regardless of the location and alignment of the charged group in the cation, particularly irrespective of whether the charged group occupies a terminal or central position in the cation structure. A comparison of the results obtained in isotropic, liquid-crystalline, and solid states shows that in the bulk materials the dynamic state of ions ranging from high reorientational and translational freedom to partial orientation and positional order to full immobilization, respectively, has no strong impact on the cation-anion hydrogen bond strength. On the other hand, nanoconfinement of ionic liquid crystals led to hydrogen bond disruption due to competing interactions of anions with a solid interface. 

Ionic liquids crystals belong to a special class of ionic liquids that exhibit thermotropic liquid-crystalline behavior. Recently, dicationic ionic liquid crystals have been reported with a cation containing two single-charged ions covalently linked by a spacer. In ionic liquid crystals, electrostatic and hydrogen bonding interactions in ionic sublayer and van der Waals interaction in hydrophobic domains are the main forces contributing to the mesophase stabilization and determining the molecular orientational order and conformation. How these properties in dicationic materials are compared to those in conventional monocationic analogs? We address this question using a combination of advanced NMR methods and DFT analysis. Dicationic salt 3,3 '-(1,6-hexanediyl)bis(1-dodecylimidazolium)dibromide was studied. Local bond order parameters of flexible alkyl side chains, linker chain, and alignment of rigid polar groups were analyzed. The dynamic spacer effectively "decouples" the motion of two ionic moieties. Hence, local order and alignment in dicationic mesophase were similar to those in analogous single-chain monocationic salts. Bond order parameters in the side chains in the dicationic smectic phase were found consistently lower compared to double-chain monocationic analogs, suggesting decreasing contribution of van der Waals forces. Overall dication reorientation in the smectic phase was characterized by low values of orientational order parameter S. With increased interaction energy in the polar domain the layered structure is stabilized despite less ordered dications. The results emphasized the trends in the orientational order in ionic liquid crystals and contributed to a better understanding of interparticle interactions driving smectic assembly in this and analogous ionic mesogens.