Densification of Ionic Liquid Molecules within a Hierarchical Nanoporous Carbon Structure Revealed by Small-Angle Scattering and Molecular Dynamics Simulation

The molecular-scale properties of the room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium bis­(trifluoromethylsulfonyl) imide, [C₄mim⁺]­[Tf₂N^–], confined in nanometer-scale carbon pores have been investigated using small-angle X-ray and neutron scattering and fully atomistic molecular dynamics simulations. [C₄mim⁺]­[Tf₂N^–] densities significantly higher than that of the bulk fluid at the same temperature and pressure result from the strong affinity of the RTIL cation with the carbon surface during the initial filling of slitlike, subnanometer micropores along the mesopore surfaces. Subsequent filling of cylindrical ∼8 nm mesopores in the mesoporous carbon matrix is accompanied by weak RTIL densification. The relative size of the micropores compared to the ion dimension, and the strong interaction between the RTIL and the slit-like micropore, disrupt the bulk RTIL structure. This results in a low-excluded volume, high-RTIL ion density configuration. The observed interfacial phenomena are simulated using a molecular dynamics model consisting of a linear combination of mesopore and micropore effects. These observations highlight the importance of including the effects of a porous substrate’s internal surface morphology, especially roughness and microporosity, on the resulting electrolyte structural properties and performance in electrical energy storage applications

Alkyl Chain Length and Temperature Effects on Structural Properties of Pyrrolidinium-Based Ionic Liquids: A Combined Atomistic Simulation and Small-Angle X-ray Scattering Study

Molecular dynamics (MD) simulations of 1-alkyl-1-methylpyrrolidinium bis­(trifluoromethanesulfonyl)­imide ([C_<i>n</i>MPy]­[Tf₂N], <i>n</i> = 3, 4, 6, 8, 10) were conducted using an all-atom model. Radial distribution functions (RDF) were computed and structure functions were generated to compare with new X-ray scattering experimental results, reported herein. The scattering peaks in the structure functions generally shift to lower <i>Q</i> values with increased temperature for all the liquids in this series. However, the first sharp diffraction peak (FSDP) in the longer alkyl chain liquids displays a marked shift to higher <i>Q</i> values with increasing temperature. Alkyl chain-dependent ordering of the polar groups and increased tail aggregation with increasing alkyl chain length were observed in the partial pair correlation functions and the structure functions. The reasons for the observed alkyl chain-dependent phenomena and temperature effects were explored

Structure of Spontaneously Formed Solid-Electrolyte Interphase on Lithiated Graphite Determined Using Small-Angle Neutron Scattering

We address the reactivity of lithiated graphite–anode material for Li-ion batteries with standard organic solvents used in batteries (ethylene carbonate and dimethyl carbonate) by following changes in neutron scattering signals. The reaction produces a nanosized layer, the solid-electrolyte interphase (SEI), on the graphite particles. We probe the structure and chemistry of the SEI using small-angle neutron scattering (SANS) and inelastic neutron scattering. The SANS results show that the SEI fills 20–30 nm sized pores, and inelastic scattering experiments with H/D substitution show that this “chemical” SEI is primarily organic in nature; that is, it contains a large amount of hydrogen. The graphite–SEI particles show surface fractal scattering characteristic of a rough particle–void interface and are interconnected. The observed changes in the SEI structure and composition provide new insight into SEI formation. The chemically formed SEI is complementary and simpler in composition to the electrochemically formed SEI, which involves a number of different reactions and products that are difficult to deconvolute

Fate of Liposomes in the Presence of Phospholipase C and D: From Atomic to Supramolecular Lipid Arrangement

Understanding the origins of lipid membrane bilayer rearrangement in response to external stimuli is an essential component of cell biology and the bottom-up design of liposomes for biomedical applications. The enzymes phospholipase C and D (PLC and PLD) both cleave the phosphorus–oxygen bonds of phosphate esters in phosphatidylcholine (PC) lipids. The atomic position of this hydrolysis reaction has huge implications for the stability of PC-containing self-assembled structures, such as the cell wall and lipid-based vesicle drug delivery vectors. While PLC converts PC to diacylglycerol (DAG), the interaction of PC with PLD produces phosphatidic acid (PA). Here we present a combination of small-angle scattering data and all-atom molecular dynamics simulations, providing insights into the effects of atomic-scale reorganization on the supramolecular assembly of PC membrane bilayers upon enzyme-mediated incorporation of DAG or PA. We observed that PC liposomes completely disintegrate in the presence of PLC, as conversion of PC to DAG progresses. At lower concentrations, DAG molecules within fluid PC bilayers form hydrogen bonds with backbone carbonyl oxygens in neighboring PC molecules and burrow into the hydrophobic region. This leads initially to membrane thinning followed by a swelling of the lamellar phase with increased DAG. At higher DAG concentrations, localized membrane tension causes a change in lipid phase from lamellar to the hexagonal and micellar cubic phases. Molecular dynamics simulations show that this destabilization is also caused in part by the decreased ability of DAG-containing PC membranes to coordinate sodium ions. Conversely, PLD-treated PC liposomes remain stable up to extremely high conversions to PA. Here, the negatively charged PA headgroup attracts significant amounts of sodium ions from the bulk solution to the membrane surface, leading to a swelling of the coordinated water layer. These findings are a vital step toward a fundamental understanding of the degradation behavior of PC lipid membranes in the presence of these clinically relevant enzymes, and toward the rational design of diagnostic and drug delivery technologies for phospholipase-dysregulation-based diseases

Fate of Liposomes in the Presence of Phospholipase C and D: From Atomic to Supramolecular Lipid Arrangement

Understanding the origins of lipid membrane bilayer rearrangement in response to external stimuli is an essential component of cell biology and the bottom-up design of liposomes for biomedical applications. The enzymes phospholipase C and D (PLC and PLD) both cleave the phosphorus–oxygen bonds of phosphate esters in phosphatidylcholine (PC) lipids. The atomic position of this hydrolysis reaction has huge implications for the stability of PC-containing self-assembled structures, such as the cell wall and lipid-based vesicle drug delivery vectors. While PLC converts PC to diacylglycerol (DAG), the interaction of PC with PLD produces phosphatidic acid (PA). Here we present a combination of small-angle scattering data and all-atom molecular dynamics simulations, providing insights into the effects of atomic-scale reorganization on the supramolecular assembly of PC membrane bilayers upon enzyme-mediated incorporation of DAG or PA. We observed that PC liposomes completely disintegrate in the presence of PLC, as conversion of PC to DAG progresses. At lower concentrations, DAG molecules within fluid PC bilayers form hydrogen bonds with backbone carbonyl oxygens in neighboring PC molecules and burrow into the hydrophobic region. This leads initially to membrane thinning followed by a swelling of the lamellar phase with increased DAG. At higher DAG concentrations, localized membrane tension causes a change in lipid phase from lamellar to the hexagonal and micellar cubic phases. Molecular dynamics simulations show that this destabilization is also caused in part by the decreased ability of DAG-containing PC membranes to coordinate sodium ions. Conversely, PLD-treated PC liposomes remain stable up to extremely high conversions to PA. Here, the negatively charged PA headgroup attracts significant amounts of sodium ions from the bulk solution to the membrane surface, leading to a swelling of the coordinated water layer. These findings are a vital step toward a fundamental understanding of the degradation behavior of PC lipid membranes in the presence of these clinically relevant enzymes, and toward the rational design of diagnostic and drug delivery technologies for phospholipase-dysregulation-based diseases