Fully Bio-Based Ionic Liquids for Green Chemical Modification of Cellulose in the Activated-State.

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".

Phase equilibrium, dynamics and rheology of phospholipid-ethanol mixtures: a combined molecular dynamics, NMR and viscometry study.

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.

Aqueous synthesis of highly functional, hydrophobic, and chemically recyclable cellulose nanomaterials through oxime ligation.

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.

Insights into cation-anion hydrogen bonding in mesogenic ionic liquids: an NMR study.

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.

Ion conformation and orientational order in a dicationic ionic liquid crystal studied by solid-state nuclear magnetic resonance spectroscopy.

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.

NMR Spectroscopic Studies of Cation Dynamics in Symmetrically-Substituted Imidazolium-Based Ionic Liquid Crystals.

Ionic liquid crystals (ILCs) present a new class of non-molecular soft materials with a unique combination of high ionic conductivity and anisotropy of physicochemical properties. Symmetrically-substituted long-chain imidazolium-based mesogenic ionic liquids exhibiting a smectic liquid crystalline phase were investigated by solid state NMR spectroscopy and computational methods. The aim of the study was to reveal the correlation between cation size and structure, local dynamics, and orientational order in the layered mesophase. The obtained experimental data are consistent with the model of a rod-shaped cation with the two chains aligned in opposite directions outward from the imidazolium core. The alignment of the core plane to the phase director and the restricted conformations of the chain segments were determined and compared to those in single-chain counterparts. The orientational order parameter S~0.5-0.6 of double-chain ionic liquid crystals is higher than that of corresponding single-chain analogues. This is compatible with the enhanced contribution of van der Waals forces to the stabilization of smectic layers. Increased orientational order for the material with Br- counterions, which exhibit a smaller ionic radius and higher ability to form hydrogen bonds as compared to that of BF4-, also indicated a non-negligible influence of electrostatic and hydrogen bonding interactions. The enhanced rod-shape character and higher orientational order of symmetrically-substituted ILCs can offer additional opportunities in the design of self-assembling non-molecular materials.

Understanding ionic mesophase stabilization by hydration: a solid-state NMR study.

The correlation between the water contribution to hydrogen bonding within ionic sublayer, mesophase order parameter, and ion translational self-diffusion in the layered ionic liquid crystalline phase is investigated. Changes in hydrogen bonding, conformational and translational dynamics, and orientational order upon hydration were followed by solid-state NMR combined with density functional theory (DFT) analysis. We observed that the smectic mesophase of monohydrated imidazolium-based ionic liquids, which was stabilized in a wider temperature range compared to that of anhydrous materials, counterintuitively exhibited a lower orientational order of organic cations. Thus the role of anisotropic alignment of cations and contribution of dispersion forces in the mesophase stability decreased upon hydration. The local dynamics of cations is controlled by the alignment of the bulky methyl-imidazolium ring, experiencing strong electrostatic and H-bond interactions in the ionic sublayer. Anisotropy of translational diffusion increased in the hydrated samples, thus supporting the layer-stabilizing effect of water. The effect of decreasing molecular order is outweighed by the contribution of water hydrogen bonding to the overall interaction energy within the ionic sublayer.

Experimental strategies for 13C-15N dipolar NMR spectroscopy in liquid crystals at the natural isotopic abundance.

Direct dipolar spin couplings are informative and sensitive probes for a wide range of dynamic processes and structural properties at atomic, molecular and supramolecular levels in liquid crystals and other anisotropic materials. Usually, heteronuclear 13C-1H dipolar couplings in liquid crystals with natural 13C abundance are measured. Recording 13C-15N NMR dipolar spectra in unlabeled materials is challenging because of the unfavorable combination of two rare isotopes. Here we design and compare various experimental strategies to measure short- and long-range heteronuclear 13C-15N dipolar couplings in liquid crystalline samples with high molecular orientational order. New techniques were developed to record 13C and 15N spectra of naturally occurring 13C-15N spin pairs with increased signal intensity and spectral resolution while suppressing the signals of the uncoupled isotopes. Highly resolved 13C-15N dipolar spectra were recorded within an experimental time of a few hours. Coupling constants in a broad range of 10-1000 Hz between spins separated by up to five chemical bonds and distances of up to 5 Å were measured. Because of their relatively low demands on radio-frequency power levels, the experiments were easy to implement using conventional high-resolution solution-state NMR hardware. Experimental data were compared to the results of density functional theory and molecular dynamics computational analyses. The presented experimental methods to characterize the dipolar couplings in unlabeled materials provide novel routes to investigate molecular structure and dynamics in mesophases.

Investigation of Melts of Polybutylcarbosilane Dendrimers by 1H NMR Spectroscopy.

Melts of polybutylcarbosilane (PBC) dendrimers from third (G3) up to sixth (G6) generations are investigated by 1H NMR spectroscopy in a wide temperature range up to 493 K. At room temperature, NMR spectra of G3-G5 dendrimers exhibit resolved, solution-like spectra ("liquid" phase). In contrast, the spectrum of the G6 dendrimer is characterized by a single unresolved broad line at whole temperature range, which supports the presence of an anomalous phase state of G6 at temperatures higher than glass transition temperature. For the first time, an unexpected transition of G5 dendrimer from a molecular liquid state to an anomalous state/phase upon temperature increase has been detected using NMR data. Specifically, an additional wide background line appears in the G5 spectrum above 473 K, and this line corresponds to a G5 state characterized by restricted molecular mobility, i.e., a state similar to the "anomalous" phase of G6 melt. The fraction of the G5 dendrimers in "anomalous" phase at 493 K is approximately 40%. Analysis of the spectral shapes suggests that changes in the G5 dendrimers are reversible with temperature.

NMR longitudinal relaxation enhancement in metal halides by heteronuclear polarization exchange during magic-angle spinning.

Orders of magnitude decrease of (207)Pb and (199)Hg NMR longitudinal relaxation times T1 upon magic-angle-spinning (MAS) are observed and systematically investigated in solid lead and mercury halides MeX2 (Me = Pb, Hg and X = Cl, Br, I). In lead(ii) halides, the most dramatic decrease of T1 relative to that in a static sample is in PbI2, while it is smaller but still significant in PbBr2, and not detectable in PbCl2. The effect is magnetic-field dependent but independent of the spinning speed in the range 200-15 000 Hz. The observed relaxation enhancement is explained by laboratory-frame heteronuclear polarization exchange due to crossing between energy levels of spin-1/2 metal nuclei and adjacent quadrupolar-spin halogen nuclei. The enhancement effect is also present in lead-containing organometal halide perovskites. Our results demonstrate that in affected samples, it is the relaxation data recorded under non-spinning conditions that characterize the local properties at the metal sites. A practical advantage of fast relaxation at slow MAS is that spectral shapes with orientational chemical shift anisotropy information well retained can be acquired within a shorter experimental time.

¹³C SPE MAS measurement of ligand concentration in compressible chromatographic beads.

A method for measuring the ligand concentration in heterogeneous materials like chromatography media is described. In this method, (13)C single pulse excitation magic angle spinning NMR experiment with broadband (1)H decoupling is used to determine the peak integrals for a butyl ligand in the spectrum of a dried chromatography medium. Within a carefully controlled protocol, those integrals compared with that of the internal reference compound dimethyl sulfone provide the required volume concentration with an accuracy of ca 2%. The effects of temperature, degree of hydration, and other experimental parameters are discussed.

Magnetic orientation of nontronite clay in aqueous dispersions and its effect on water diffusion.

The diffusion rate of water in dilute clay dispersions depends on particle concentration, size, shape, aggregation and water-particle interactions. As nontronite clay particles magnetically align parallel to the magnetic field, directional self-diffusion anisotropy can be created within such dispersion. Here we study water diffusion in exfoliated nontronite clay dispersions by diffusion NMR and time-dependant 1H-NMR-imaging profiles. The dispersion clay concentration was varied between 0.3 and 0.7 vol%. After magnetic alignment of the clay particles in these dispersions a maximum difference of 20% was measured between the parallel and perpendicular self-diffusion coefficients in the dispersion with 0.7 vol% clay. A method was developed to measure water diffusion within the dispersion in the absence of a magnetic field (random clay orientation) as this is not possible with standard diffusion NMR. However, no significant difference in self-diffusion coefficient between random and aligned dispersions could be observed.

Comparative study of local structure of two cyanobiphenyl liquid crystals by molecular dynamics method.

Fully-atomistic molecular dynamics simulations were carried out on two similar cyanobiphenyl nematogens, HO-6OCB and 7OCB, in order to study effects of hydrogen bonds on local structure of liquid crystals. Comparable length of these two molecules provides more evident results on the effects of hydrogen bonding. The analysis of radial and cylindrical distribution functions clearly shows the differences in local structure of two mesogens. The simulations showed that anti-parallel alignment is preferable for the HO-6OCB. Hydrogen bonds between OH-groups are observed for 51% of HO-6OCB molecules, while hydrogen bonding between CN- and OH-groups occurs only for 16% of molecules. The lifetimes of H-bonds differ due to different mobility of molecular fragments (50 ps for N⋅⋅⋅H-O and 41 ps for O⋅⋅⋅H-O). Although the standard Optimized Potentials for Liquid Simulations - All-Atom force field cannot reproduce some experimental parameters quantitatively (order parameters are overestimated, diffusion coefficients are not reproduced well), the comparison of relative simulated results for the pair of mesogens is nevertheless consistent with the same relative experimental parameters. Thus, the comparative study of simulated and experimental results for the pair of similar liquid crystals still can be assumed plausible.

Phase transitions and chain dynamics of surfactants intercalated into the galleries of naturally occurring clay mineral magadiite.

We investigate conformational dynamics and phase transitions of surfactant molecules confined in the layered galleries of the organo-modified, natural polysilicate clay, magadiite. We have shown that our approach to studying this class of materials is capable of delivering detailed information on the molecular mobility of the confined molecules. From the analysis of the measured heteronuclear dipolar couplings, the orientational order parameters of the C-H bonds along the hydrocarbon chain have been determined. Three phases have been observed in the nanocomposite, characterized by distinct dynamical states of the surfactant. At room temperature, restricted mobility of the molecules led to the adoption of an essentially all-trans conformation by the chains. This behavior can be described by a model incorporating small-angle wobbling around the long molecular axes of the chains. Upon heating, dynamic transformation takes place, resulting in a rotator type solid phase where molecules in extended all-trans conformations undergo fast and unrestricted rotation about their respective symmetry axes. The second phase transition is associated with chain melting and the onset of translational dynamics and results in an essentially liquid-crystalline-like state of the organic component. The mobility of the surfactant is one of the key factors facilitating the efficient penetration of macromolecules in the process of preparing of polymer/organoclay nanocomposites. The exploration of dynamic properties of the functionalizing organic layer should provide important input into the improved design of new organic-inorganic hybrid materials.

Suppressing magnetization exchange effects in stimulated-echo diffusion experiments.

Exchange of nuclear magnetization between spin pools, either by chemical exchange or by cross-relaxation or both, has a significant influence on the signal attenuation in stimulated-echo-type pulsed field gradient experiments. Hence, in such cases the obtained molecular self-diffusion coefficients can carry a large systematic error. We propose a modified stimulated echo pulse sequence that contains T2-filters during the z-magnetization store period. We demonstrate, using a common theoretical description for chemical exchange and cross-relaxation, that these filters suppress the effects of exchange on the diffusional decay in that frequent case where one of the participating spin pools is immobile and exhibits a short T2. We demonstrate the performance of this experiment in an agarose/water gel. We posit that this new experiment has advantages over other approaches hitherto used, such as that consisting of measuring separately the magnetization exchange rate, if suitable by Goldman-Shen type experiments, and then correcting for exchange effects within the framework of a two-site exchange model. We also propose experiments based on selective decoupling and applicable in systems with no large T2 difference between the different spin pools.

Wood microstructure explored by anisotropic 1H NMR line broadening: experiments and numerical simulations.

The cellular structure of wood, which is highly anisotropic along its main growth directions, is responsible for the observed anisotropy in its physical and mechanical properties that depend in a complex manner on the moisture content. Here, we demonstrate that the (1)H NMR spectra of wood from Norway spruce exhibit a strong and characteristic dependence on the direction of the sample relative to the applied magnetic field. By comparing spectra recorded at different magnetic-field strengths, we show that this variation is caused by the magnetic-field distribution created by the anisotropic and inhomogeneous distribution of matter and thereby magnetic susceptibility. On the basis of the observations that (i) the recorded spectral peak predominantly arises from translationally mobile water molecules and (ii) the spectral broadening is large if the long axis of the wood tracheid cells is perpendicular to the magnetic field, we set out to test the hypothesis that it is the susceptibility variation on the tracheid length scale that is responsible for the observed spectral features. To verify this, we numerically calculate in a discrete grid approximation the NMR line shapes obtained in realistic tracheid models, and we find that the calculated NMR line shapes are in good agreement with the corresponding experimental ones. We envisage the application of these findings for revealing the inhomogeneous distribution of water and its molecular properties in wood and wood-based materials at varying degrees of humidity.

Constant-time chemical-shift selective imaging.

We demonstrate that chemical-shift-selective constant-time imaging (CTI) can be performed by simply inserting selective saturation into the original imaging pulse sequence. The performance of the proposed method is illustrated by (7)Li CTI imaging in a battery model that contains both Li metal electrodes and an electrolyte containing a dissolved Li salt.

Anisotropic self-diffusion in nematic, smectic-A, and reentrant nematic phases.

The nature of the reentrant nematic phase has been actively investigated both experimentally and theoretically during the past few decades. Most studies concluded that, as concerning molecular dynamics, a reentrant nematic phase is essentially analogous to a conventional nematic one. Recent computer simulations [Mazza et al., Phys. Rev. Lett. 105, 227802 (2010)], however, predicted molecular translational self-diffusion along the phase director that was dominated by a collective transport mode and was, relative to that observed in a conventional nematic phase, enhanced by an order of magnitude. In the present work, the principal components of the diffusion tensor in a reentrant nematic phase are determined experimentally and compared to those in conventional nematic and smectic-A phases. We find that the temperature dependence of the translational diffusion in the two nematic phases, within experimental error, follows a uniform trend and can be adequately described in terms of available diffusion models in nematics. Hence, we find no evidence for enhanced diffusion but confirm instead the similarity of conventional and reentrant nematic phases with respect to molecular translational dynamics.

Dynamic properties of water in silicalite-1 powder.

Self-diffusion of D(2)O in partially filled silicalite-1 crystals was studied at 25°C by (2)H nuclear magnetic resonance (NMR) with bipolar field gradient pulses and longitudinal Eddy-current-delay. For the first time, reliable experimental diffusion data for this system were obtained. Analysis of NMR diffusion decays revealed the presence of a continuous distribution of apparent self-diffusion coefficients (SDCs) of water, ranging from 10(-7) to ∼10(-10) m(2)/s, which include values much higher and lower than that of bulk water (∼10(-9) m(2)/s) in liquid phase. The observed distribution of SDC changes with variation of the diffusion time in the range of 10-200 ms. A two-site Kärger exchange model was successfully fitted to the data. Finally, the water distribution and exchange in silicalite-1 pores were described by taking into account (a) a gas-like phase in the zeolite pores, a gas-like phase in mesopores and an intercrystalline gas-like phase and (b) intercrystalline liquid droplets with intermediate exchange rate with the other phases. The other phases experience fast exchange on the NMR diffusion time scale. Diffusion coefficients and mean residence times of water in some of these states were estimated.

Polymer swelling, drug mobilization and drug recrystallization in hydrating solid dispersion tablets studied by multinuclear NMR microimaging and spectroscopy.

Despite the advantages offered by solid dispersions, the marketed products based on this technology are few. The most frequent concern is the stability of the amorphous drug. The state of the drug in solid dispersions is, in general, poorly characterized as the number of characterization techniques available to monitor nanometer-sized drug particles embedded in a matrix are limited. Here we present a combination of localized NMR spectroscopic and NMR imaging techniques which allow in situ monitoring of the state of the drug during tablet disintegration and dissolution. (19)F NMR relaxation is shown to be sensitive to both the crystalline/amorphous state and the size of the model nanoparticles made of the drug substance flutamide. The time course of drug mobilization and recrystallization is detected with spatial resolution within swelling solid dispersion tablets. Comparing results from spatially resolved (19)F, (2)H and (1)H NMR experiments, recrystallization is related to its enabling factors such as local hydration level and local mobility of the polymer matrix. The initially amorphous drug may recrystallize either by nanoparticle coalescence or by ripening of crystalline grains.