Modulation of Phase Behavior and Microscopic Dynamics in Cationic Vesicles by 1-Decyl-3-methylimidazolium Bromide.

Synthetic cationic lipids have garnered significant attention as promising candidates for gene/DNA transfection in therapeutic applications. The phase behavior of the vesicles formed by these lipids is intriguing, revealing intricate connections to the structure and dynamics of the membrane. These phenomena emerge from the complex interplay between hydrophobic and electrostatic interactions of the lipids. In this study, we explore the impact of an ionic liquid-based surfactant, 1-decyl-3-methylimidazolium bromide (DMIM[Br]), on the structural, dynamical, and phase behavior of cationic dihexadecyldimethylammonium bromide (DHDAB) vesicles. Our investigations indicate that the addition of DMIM[Br] increases the vesicle size while thinning the membrane. Further, DMIM[Br] also induces substantial changes in the membrane phase behavior. At 10 and 25 mol %, DMIM[Br] eliminates the pre-transition from coagel to intermediate crystalline (IC) phase and decreases the onset temperature of the main phase transition to the fluid phase. In the cooling cycle, the addition of DMIM[Br] further induces the formation of an intermediate gel phase. This behavior is reminiscent of the non-synchronous ordering observed in the DODAB membrane, a longer-chain counterpart of DHDAB. Interestingly, at 40 mol % of DMIM[Br], the formation of the intermediate gel phase is largely suppressed. Neutron scattering data provide evidence that the addition of DMIM[Br] enhances lipid mobility in coagel and fluid phases, suggesting that DMIM[Br] acts as a plasticizer, enhancing membrane fluidity across all of the phases. Our findings infer that DMIM[Br] modulates the membrane's phase behavior and fluidity, two essential ingredients for the efficient transport of cargo, by controlling the balance of electrostatic and hydrophobic interactions.

Microscopic temperature-dependent structural dynamics in polymer nanocomposites: role of the graft-matrix chain interfacial entropic effect.

We present a systematic study of the structural dynamics in bulk entropic polymer nanocomposites (PNCs) with deuterated-polymer-grafted nanoparticles (DPGNPs) using quasi-elastic neutron scattering (QENS). We observe that the wave-vector-dependent relaxation dynamics depend on the entropic parameter f as well as the length scale being probed. The entropic parameter can be defined in terms of the grafted-to-matrix polymer molecular weight ratio and controls the extent of matrix chain penetration into the graft. Dynamical cross-over from Gaussian to non-Gaussian behavior at the wave vector Qc, which depends on temperature and f, was observed. Further insight into the underlying microscopic mechanism responsible for the observed behavior revealed that when interpreted using a jump-diffusion model, in addition to the speeding-up in local chain dynamics, the elementary distance over which sections of the chain hop is strongly dependent on f. Interestingly, we also observe dynamic heterogeneity (DH) in the studied systems, characterized by the non-Gaussian parameter α2, which reduces for a high-f (f = 0.225) sample compared with the pristine host polymer, indicating reduced dynamical heterogeneity, while it is mostly unchanged for the low-f sample. The results highlight that, unlike enthalpic PNCs, entropic PNCs with DPGNPs can modify the host polymer dynamics due to the subtle balance of interactions that occur at different length scales in the matrix.

Universal dynamical onset in water at distinct material interfaces.

Interfacial water remains liquid and mobile much below 0 °C, imparting flexibility to the encapsulated materials to ensure their diverse functions at subzero temperatures. However, a united picture that can describe the dynamical differences of interfacial water on different materials and its role in imparting system-specific flexibility to distinct materials is lacking. By combining neutron spectroscopy and isotope labeling, we explored the dynamics of water and the underlying substrates independently below 0 °C across a broad range of materials. Surprisingly, while the function-related anharmonic dynamical onset in the materials exhibits diverse activation temperatures, the surface water presents a universal onset at a common temperature. Further analysis of the neutron experiment and simulation results revealed that the universal onset of water results from an intrinsic surface-independent relaxation: switching of hydrogen bonds between neighboring water molecules with a common energy barrier of ∼35 kJ mol-1.

Disentangling water, ion and polymer dynamics in an anion exchange membrane.

Semipermeable polymeric anion exchange membranes are essential for separation, filtration and energy conversion technologies including reverse electrodialysis systems that produce energy from salinity gradients, fuel cells to generate electrical power from the electrochemical reaction between hydrogen and oxygen, and water electrolyser systems that provide H2 fuel. Anion exchange membrane fuel cells and anion exchange membrane water electrolysers rely on the membrane to transport OH- ions between the cathode and anode in a process that involves cooperative interactions with H2O molecules and polymer dynamics. Understanding and controlling the interactions between the relaxation and diffusional processes pose a main scientific and critical membrane design challenge. Here quasi-elastic neutron scattering is applied over a wide range of timescales (100-103 ps) to disentangle the water, polymer relaxation and OH- diffusional dynamics in commercially available anion exchange membranes (Fumatech FAD-55) designed for selective anion transport across different technology platforms, using the concept of serial decoupling of relaxation and diffusional processes to analyse the data. Preliminary data are also reported for a laboratory-prepared anion exchange membrane especially designed for fuel cell applications.

Universality of Time-Temperature Scaling Observed by Neutron Spectroscopy on Bottlebrush Polymers.

The understanding of materials requires access to the dynamics over many orders of magnitude in time; however, single analytical techniques are restricted in their respective time ranges. Assuming a functional relationship between time and temperature is one viable tool to overcome these limits. Despite its frequent usage, a breakdown of this assertion at the glass-transition temperature is common. Here, we take advantage of time- and length-scale information in neutron spectroscopy to show that the separation of different processes is the minimum requirement toward a more universal picture at, and even below, the glass transition for our systems. This is illustrated by constructing the full proton mean-square displacement for three bottlebrush polymers from femto- to nanoseconds, with simultaneous information on the partial contributions from segmental relaxation, methyl group rotation, and vibrations. The information can be used for a better analysis of results from numerous techniques and samples, improving the overall understanding of materials properties.

Progress in neutron techniques: towards improved polymer electrolyte membranes for energy devices.

Design and implementation of advanced membrane formulations for selective transport of ions and molecular species are critical for creating the next generations of fuel cells and separation devices. It is necessary to understand the detailed transport mechanisms over time- and length-scales relevant to the device operation, both in laboratory models and in working systems under realistic operational conditions. Neutron scattering techniques including quasi-elastic neutron scattering, reflectivity and imaging are implemented at beamline stations at reactor and spallation source facilities worldwide. With the advent of new and improved instrument design, detector methodology, source characteristics and data analysis protocols, these neutron scattering techniques are emerging as a primary tool for research to design, evaluate and implement advanced membrane technologies for fuel cell and separation devices. Here we describe these techniques and their development and implementation at the ILL reactor source (Institut Laue-Langevin, Grenoble, France) and ISIS Neutron and Muon Spallation source (Harwell Science and Technology Campus, UK) as examples. We also mention similar developments under way at other facilities worldwide, and describe approaches such as combining optical with neutron Raman scattering and x-ray absorption with neutron imaging and tomography, and carrying out such experiments in specialised fuel cells designed to mimic as closely possible actualoperandoconditions. These experiments and research projects will play a key role in enabling and testing new membrane formulations for efficient and sustainable energy production/conversion and separations technologies.

Ammonia Storage in Hydrogen Bond-Rich Microporous Polymers.

The fascinating structural flexibility of porous polymers is highly attractive because it can result in optimized materials with specific host-guest interactions. Nevertheless, the fundamental mechanisms responsible for controlling the weak interactions of these hydrogen bond-rich networks-essential for developing smart task-specific materials used in recognition, capture, and sequestration processes-remain unexplored. Herein, by systematically comparing performance changes between poly(amic acid) (PAA)- and polycyclic imide (PI)-based porous polymers before and after NH3 adsorption, the role of hydrogen bonds in conformational lability and responsiveness toward guest molecules is highlighted. By combining thermal gravimetric analysis with neutron spectroscopy supported by DFT calculations, we demonstrate that PAA's chemical and physical stability is enhanced by the presence of stronger host-guest interactions. This observation also emphasizes the idea that efficient adsorption relies on having a high number of sites, upon which gas molecules can adsorb with greater affinity via strong hydrogen bonding interactions.

Short-Time Dynamics of PDMS-g-PDMS Bottlebrush Polymer Melts Investigated by Quasi-Elastic Neutron Scattering.

We have studied the short-time dynamical behavior of polydimethylsiloxane (PDMS) bottlebrush polymers, PDMS-g-PDMS. The samples have similar backbone lengths but different side-chain lengths, resulting in a shape transition. Quasi-elastic neutron scattering was used to observe the dynamical changes inherent to these structural changes. The combination of data from three spectrometers enabled to follow the dynamics over broad frequency and temperature ranges, which included segmental relaxations and more localized motions. The latter, identified as the methyl group rotation, is described by a threefold jump model and shows higher activation energies compared to linear PDMS. The segmental relaxation times, τs, decrease with increasing molecular weight of the side chains but increase with momentum transfer, Q, following a power law, which suggests a non-Gaussian behavior for bottlebrush polymers.

Anomalous sub-diffusion of water in biosystems: From hydrated protein powders to concentrated protein solution to living cells.

Water is essential to life and its translational motion in living systems mediates various biological processes, including transportation of function-required ingredients and facilitating the interaction between biomacromolecules. By combining neutron scattering and isotopic labeling, the present work characterizes translational motion of water on a biomolecular surface, in a range of systems: a hydrated protein powder, a concentrated protein solution, and in living Escherichia coli (E. coli) cells. Anomalous sub-diffusion of water is observed in all samples, which is alleviated upon increasing the water content. Complementary molecular dynamics simulations and coarse-grained numerical modeling demonstrated that the sub-diffusive behavior results from the heterogeneous distribution of microscopic translational mobility of interfacial water. Moreover, by comparing the experimental results measured on E. coli cells with those from a concentrated protein solution with the same amount of water, we show that water in the two samples has a similar average mobility, however the underlying distribution of motion is more heterogeneous in the living cell.

Aquaporin-like water transport in nanoporous crystalline layered carbon nitride.

Designing next-generation fuel cell and filtration devices requires the development of nanoporous materials that allow rapid and reversible uptake and directed transport of water molecules. Here, we combine neutron spectroscopy and first-principles calculations to demonstrate rapid transport of molecular H2O through nanometer-sized voids ordered within the layers of crystalline carbon nitride with a polytriazine imide structure. The transport mechanism involves a sequence of molecular orientation reversals directed by hydrogen-bonding interactions as the neutral molecules traverse the interlayer gap and pass through the intralayer voids that show similarities with the transport of water through transmembrane aquaporin channels in biological systems. The results suggest that nanoporous layered carbon nitrides can be useful for developing high-performance membranes.

The Effect of an Intramembrane Light-Actuator on the Dynamics of Phospholipids in Model Membranes and Intact Cells.

The noncovalent intercalation of amphiphilic molecules in the lipid membrane can be exploited to modulate efficiently the physical status of the membrane. Such effects are largely employed in a range of applications, spanning from drug-delivery to therapeutics. In this context, we have very recently developed an intramembrane photo-actuator consisting of an amphiphilic azobenzene molecule, namely ZIAPIN2. The selective photo-isomerization occurring in the lipid bilayer induces a photo-triggered change in the membrane thickness and capacitance, eventually permitting to evoke light-induced neuronal firing both in vitro and in vivo. Here, we present a study on the dynamical perturbation in the lipid membrane caused by ZIAPIN2 and its vehicle solvent, dimethyl sulfoxide. Effects on the dynamics occurring in the picosecond time range and at the molecular level are probed using quasi-elastic neutron scattering. By coupling experiments carried out both on model membranes and intact cells, we found that DMSO leads to a general retardation of the dynamics within a more dynamically ordered landscape, a result that we attribute to the dehydration at the interface. On the other hand, ZIAPIN2 partitioning produces a general softening of the bilayer owing to its interaction with the lipids. These data are in agreement with our recent studies, which indicate that the efficacy of ZIAPIN2 in triggering cellular signalling stems from its ability to mechanically perturb the bilayer as a whole, by forming light-sensitive membrane spanning dimers.

Imidazolium-based ionic liquids cause mammalian cell death due to modulated structures and dynamics of cellular membrane.

Here, we report the toxic effects of various imidazolium-based ionic liquids (ILs) with varying hydrocarbon chain lengths, on different human cell lines. Multiple biological assays have shown that the ILs with long hydrocarbon chains have stronger adverse effect especially on human liver cancer cells (Huh-7.5 cells). Further, our study has confirmed that the ILs induce necrosis dependent cell death and that it is related to cell membrane damage. To understand the molecular mechanism of such an effect, the cellular membranes were mimicked as lipid monolayers formed at the air-water interface and then as lipid bilayer vesicles. The pressure area-isotherms measured from the monolayer have shown that the interaction of ILs with the lipid layer is energetically favourable. The addition of these ILs reduces the in-plane elasticity of the self-assembled molecular layer. Quasielastic neutron scattering data clearly indicate that ILs in liver lipid vesicles significantly affects the dynamics of the lipid, in particular, the lateral motion of the lipids. It has been concluded that the mammalian cell death induced by these ILs is due to the modulated structure and altered physical properties of the cellular membrane.

In Vivo Water Dynamics in Shewanella oneidensis Bacteria at High Pressure.

Following observations of survival of microbes and other life forms in deep subsurface environments it is necessary to understand their biological functioning under high pressure conditions. Key aspects of biochemical reactions and transport processes within cells are determined by the intracellular water dynamics. We studied water diffusion and rotational relaxation in live Shewanella oneidensis bacteria at pressures up to 500 MPa using quasi-elastic neutron scattering (QENS). The intracellular diffusion exhibits a significantly greater slowdown (by -10-30%) and an increase in rotational relaxation times (+10-40%) compared with water dynamics in the aqueous solutions used to resuspend the bacterial samples. Those results indicate both a pressure-induced viscosity increase and slowdown in ionic/macromolecular transport properties within the cells affecting the rates of metabolic and other biological processes. Our new data support emerging models for intracellular organisation with nanoscale water channels threading between macromolecular regions within a dynamically organized structure rather than a homogenous gel-like cytoplasm.

Modulating proton diffusion and conductivity in metal-organic frameworks by incorporation of accessible free carboxylic acid groups.

Three multi-carboxylic acid functionalised ligands have been designed, synthesised and utilised to prepare the new barium-based MOFs, MFM-510, -511, and -512, which show excellent stability to water-vapour. MFM-510 and MFM-511 show moderate proton conductivities (2.1 × 10-5 and 5.1 × 10-5 S cm-1, respectively) at 99% RH and 298 K, attributed to the lack of free protons or hindered proton diffusion within the framework structures. In contrast, MFM-512, which incorporates a pendant carboxylic acid group directed into the pore of the framework, shows a two orders of magnitude enhancement in proton conductivity (2.9 × 10-3 S cm-1). Quasi-elastic neutron scattering (QENS) suggests that the proton dynamics of MFM-512 are mediated by "free diffusion inside a sphere" confirming that incorporation of free carboxylic acid groups within the pores of MOFs is an efficient albeit synthetically challenging strategy to improve proton conductivity.

Nanostructuration of ionic liquids: impact on the cation mobility. A multi-scale study.

When probed at the macroscopic scale, Ionic Liquids (ILs) behave as highly dissociated (i.e. strong) electrolytes while, at the molecular scale, they show clear characteristics of weak ionic solutions. The multi-scale analysis we report in this paper reconciles these apparently at odds behaviors. We investigate by quasi-elastic neutron scattering (QENS) and neutron spin-echo (NSE), the nanometer/nanosecond dynamics of OMIM-BF4, an imidazolium-based IL showing strong nanostructuration. We also probe the same IL on the microscopic (µm and ms) scale by pulsed field gradient NMR. To interpret the neutron data, we introduce a new physical model to account for the dynamics of the side-chains and for the diffusion of the whole molecule. This model describes the observables over the whole and unprecedented investigated spatial ([0.15-1.65] Å-1) and time ([0.5-2000] ps) ranges. We arrive at a coherent and unified structural/dynamical description of the local cation dynamics: a localized motion within the IL nanometric domains is combined with a genuine long-range translational motion. The QENS, NSE and NMR experiments describe the same long-range translational process, but probed at different scales. The associated diffusion coefficients are more than one order of magnitude different. We show how this apparent discrepancy is a manifestation of the IL nanostructuration.

How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO2 nanoparticles? A quasi-elastic neutron scattering study.

Motions of molecules adsorbed to surfaces may control the rate of charge transport within monolayers in systems such as dye sensitized solar cells. We used quasi-elastic neutron scattering (QENS) to evaluate the possible dynamics of two small dye moieties, isonicotinic acid (INA) and bis-isonicotinic acid (BINA), attached to TiO2 nanoparticles via carboxylate groups. The scattering data indicate that moieties are immobile and do not rotate around the anchoring groups on timescales between around 10 ps and a few ns (corresponding to the instrumental range). This gives an upper limit for the rate at which conformational fluctuations can assist charge transport between anchored molecules. Our observations suggest that if the conformation of larger dye molecules varies with time, it does so on longer timescales and/or in parts of the molecule which are not directly connected to the anchoring group. The QENS measurements also indicate that several layers of acetonitrile solvent molecules are immobilized at the interface with the TiO2 on the measurement time scale, in reasonable agreement with recent classical molecular dynamics results.

Methyl tunnelling of adsorbed methoxy on alumina catalysts.

The aim of this paper is to investigate whether the methyl group of the adsorbed methoxy intermediate on industrial grade alumina catalysts undergoes rotational tunnelling on the wavenumber energy scale. The data show that this is clearly the case for a fraction of the methyl groups and potentially allows the subtle intermolecular interactions between adsorbed species and catalyst to be probed through the exponential dependence of the tunnel frequency on the rotational potential.

The dynamics of methylammonium ions in hybrid organic-inorganic perovskite solar cells.

Methylammonium lead iodide perovskite can make high-efficiency solar cells, which also show an unexplained photocurrent hysteresis dependent on the device-poling history. Here we report quasielastic neutron scattering measurements showing that dipolar CH3NH3(+) ions reorientate between the faces, corners or edges of the pseudo-cubic lattice cages in CH3NH3PbI3 crystals with a room temperature residence time of ∼14 ps. Free rotation, π-flips and ionic diffusion are ruled out within a 1-200-ps time window. Monte Carlo simulations of interacting CH3NH3(+) dipoles realigning within a 3D lattice suggest that the scattering measurements may be explained by the stabilization of CH3NH3(+) in either antiferroelectric or ferroelectric domains. Collective realignment of CH3NH3(+) to screen a device's built-in potential could reduce photovoltaic performance. However, we estimate the timescale for a domain wall to traverse a typical device to be ∼0.1-1 ms, faster than most observed hysteresis.