The uniform size and complex chemical topology of the pores formed by self-assembled amphiphilic molecules such as liquid crystals make them promising candidates for selective separations. In this work, we observe the transport of water, sodium ions, and 20 small polar solutes within the pores of a lyotropic liquid crystal (LLC) membrane using atomistic molecular simulations. We find that the transport of a species is dependent not only on molecular size but also on chemical functionality. The membrane's inhomogeneous composition gives rise to radially dependent transport mechanisms with respect to the pore centers. We observe that all solutes perform intermittent hops between lengthy periods of entrapment. Three different trapping mechanisms are responsible for this behavior. First, solutes that drift out of the pore can become entangled among the dense monomer tails. Second, solutes can donate hydrogen bonds to the monomer head groups. Third, solutes can coordinate with sodium counterions. The degree to which a solute is affected by each mechanism is dependent on the chemical functionality of the solute. Using the insights developed in this study, we can begin to think about how to redesign existing LLC membranes to perform solute-specific separations.

The substitution of natural, bio-based and/or biodegradable polymers for those of petrochemical origin in consumer formulations has become an active area of research and development as the sourcing and destiny...

Periodic, nanostructured porous polymer membranes made from the cross-linked inverted hexagonal phase of self-assembled lyotropic liquid crystals (LLCs) are a promising class of materials for selective separations. In this work, we investigate an experimentally characterized LLC polymer membrane using atomistic molecular modeling. In particular, we compare simulated X-ray diffraction (XRD) patterns with experimental XRD data to quantify and understand the differences between simulation and experiment. We find that the nanopores are likely composed of five columns of stacked LLC monomers which surround each hydrophilic core. Evidence suggests that these columns likely move independently of each other over longer time scales than accessible via atomistic simulation. We also find that wide-angle X-ray scattering structural features previously attributed to monomer tail tilt are likely instead due to ordered tail packing. Although this system has been reported as dry, we show that small amounts of water are necessary to reproduce all features from the experimental XRD pattern because of asymmetries introduced by hydrogen bonds between the monomer head groups and water molecules. Finally, we explore the composition and structure of the nanopores and reveal that there exists a composition gradient rather than an abrupt partition between the hydrophilic and hydrophobic regions. A caveat is that the time scales of the dynamics are extremely long for this system, resulting in simulated structures that appear too ordered, thus requiring careful examination of the metastable states observed in order to draw any conclusions. The clear picture of the nanoscopic structure of these membranes provided in this study will enable a better understanding of the mechanisms of small-molecule transport within these nanopores.

Commercially available reverse osmosis and forward osmosis thin-film composite membranes were assessed for long-term chemical stability when immersed in 10 molal N,N-dimethylcyclohexylammonium hydrogen carbonate draw solution, a model switchable polarity solvent draw solute for forward osmosis. Membrane performance was monitored with reverse osmosis testing, including rejection of 2000 ppm sodium chloride (NaCl), for three commercial reverse osmosis membranes-Dow BW30, SW30HR, and SW30HR with polyester backing layer removed-and a commercial forward osmosis membrane (HTI TFC). The RO membranes were observed to be mostly unaffected by exposures up to 90 days while the HTI TFC suffered a sharp increase in both water permeance and sodium chloride permeability, manifesting itself as a reduction in intrinsic rejection of NaCl from 95% to 82%. The as-received HTI TFC membrane was characterized for osmotic water flux, where it was found the water flux was very insensitive to draw solute concentration in both the pressureretarded osmosis and forward osmosis operating modes. Reverse permeation of the draw solute was highly variable, despite lower variability in the forward water flux. Forward osmosis desalination of a 0.5 molal sodium chloride feed with the HTI TFC membrane and 10 molal draw solution indicated higher rejection (ca. 98.7) than under reverse osmosis testing, albeit with lower flux and the presence of reverse permeation of the draw solute. The overall results imply that a forward

Appropriate time series modeling of complex diffusion in soft matter systems on the microsecond time scale can provide a path toward inferring transport mechanisms and predicting bulk properties characteristic of much longer time scales. In this work we apply nonparametric Bayesian time series analysis, more specifically the sticky hierarchical Dirichlet process autoregressive hidden Markov model (HDP-AR-HMM) to solute center-of-mass trajectories generated from long molecular dynamics (MD) simulations in a cross-linked inverted hexagonal phase lyotropic liquid crystal (LLC) membrane in order to automatically detect a variety of solute dynamical modes. We can better understand the mechanisms controlling these dynamical modes by grouping the states identified by the HDP-AR-HMM into clusters based on multiple metrics aimed at distinguishing solute behavior based on their fluctuations, dwell times in each state, and positions within the inhomogeneous membrane structure. We analyze predominant clusters in order to relate their dynamical parameters to physical interactions between solutes and the membrane. Along with parameters of individual states, the HDP-AR-HMM simultaneously infers a transition matrix which allows us to stochastically propagate solute behavior from all of the independent trajectories onto arbitrary length time scales while still preserving the qualitative behavior characteristic of the MD trajectories. This affords a direct connection to important macroscopic observables used to characterize performance like solute flux and selectivity. This work provides a promising way to simultaneously identify transport mechanisms in nanoporous materials and project complex diffusive behavior on long time scales. Our enhanced understanding of the diverse range of solute behavior allows us to hypothesize design changes to LLC monomers aimed toward controlling the rates of solute passage, thus improving the selective performance of LLC membranes.