Amphiphilic Bilayer Research Articles

Vesicles exhibit high-performance removal of per-and polyfluoroalkyl substances (PFAS) depending on their hydrophobic groups

The removal of per- and polyfluoroalkyl substances (PFAS) from drinking water is urgently needed. Here, we demonstrated high performance of vesicles on PFAS adsorption. Vesicles used in this study were enclosed amphiphile bilayers keeping their hydrophobic groups inside and their hydrophilic groups outside in water. The distribution coefficient Kd of perfluorooctane sulfonic acid (PFOS) for vesicles was 5.3 × 105 L/kg, which is higher than that for granulated activated carbon (GAC), and Kd of perfluorooctanoic acid (PFOA) for vesicles was 103–104 L/kg. The removal efficiencies of PFOA and PFOS adsorption on DMPC vesicles were 97.1 ± 0.1% and 99.4 ± 0.2%, respectively. The adsorption behaviors of PFOA and PFOS on vesicles were investigated by changing the number of cis-double bonds in the hydrophobic chains of the vesicle constituents. Moreover, vesicles formed by membranes in the different phases were also tested. The results revealed that, when vesicles are formed of a membrane in the liquid-crystalline (liquid-like) phase, the adsorption amounts of both PFOA and PFOS increased as the cis-double bond in the hydrocarbon chains decreased, which is considered due to molecular shape similarity. When vesicles are formed of a membrane in the gel (solid-like) phase, they do not adsorb PFAS as much as in the liquid-crystalline phase, even though the hydrocarbon chains do not have any cis-double bond. Our findings demonstrate that vesicles can be utilized as PFAS adsorbents by optimizing the structure of vesicle constituents and their thermodynamical phase. Indeed, the vesicles (DMPC) were demonstrated that they can adsorb PFOA and PFOS, and be coagulated by a coagulant even in environmental water. The coagulation will enable the removal of PFOA and PFOS from the water after adsorption.

Protonation of palmitic acid embedded in DPPC lipid bilayers obscures detection of ripple phase by FTIR spectroscopy

The transformation of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipid bilayers from the gel (Lβ′) to the fluid (Lα) phase involves an intermediate ripple (Pβ′) phase forming a few degrees below the main transition temperature (Tm). While the exact cause of bilayer rippling is still debated, the presence of amphiphilic molecules, pH, and lipid bilayer architecture are all known to influence (pre)transition behavior. In particular, fatty acid chains interact with hydrophobic lipid tails, while the carboxylic groups simultaneously participate in proton transfer with interfacial water in the polar lipid region which is controlled by the pH of the surrounding aqueous medium. The molecular-level variations in the DPPC ripple phase in the presence of 2% palmitic acid (PA) were studied at pH levels 4.0, 7.3, and 9.1, where PA is fully protonated, partially protonated, or fully deprotonated. Bilayer thermotropic behavior was investigated by differential scanning calorimetry (DSC) and Fourier-transform infrared (FTIR) spectroscopy which agreed in their characterization of (pre)transition at pH of 9.1, but not at pH 4.0 and especially not at 7.3. Owing to the different insertion depths of protonated and deprotonated PA, along with the ability of protonated PA to undergo flip-flop in the bilayer, these two forms of PA show a different hydration pattern in the interfacial water layer. Finally, these results demonstrated the hitherto undiscovered potential of FTIR spectroscopy in the detection of the events occurring at the surface of lipid bilayers that obscure the low-cooperativity phase transition explored in this work.

Myelin Surfactant Assemblies as Dynamic Pathways Guiding the Growth of Electrodeposited Copper Dendrites.

Self-organization of inorganic matter enables bottom-up construction of materials with target shapes suited to their function. Positioning the building blocks in the growth process involves a well-balanced interplay of the reaction and diffusion. Whereas (supra)molecular structures have been used to template such growth processes, we reasoned that molecular assemblies can be employed to actively create concentration gradients that guide the deposition of solid, wire-like structures. The core of our approach comprises the interaction between myelin assemblies that deliver copper(II) ions to the tips of copper dendrites, which in turn grow along the Cu2+ gradient upon electrodeposition. First, we successfully include Cu2+ ions among amphiphile bilayers in myelin filaments, which grow from tri(ethylene glycol) monododecyl ether (C12E3) source droplets over air-water interfaces. Second, we characterize the growth of dendritic copper structures upon electrodeposition from a negative electrode at the sub-mM Cu2+ concentrations that are anticipated upon release from copper(II)-loaded myelins. Third, we assess the intricate growth of copper dendrites upon electrodeposition, when combined with copper(II)-loaded myelins. The myelins deliver Cu2+ at a negative electrode, feeding copper dendrite growth upon electrodeposition. Intriguingly, the copper dendrites follow the Cu2+ gradient toward the myelins and grow along them toward the source droplet. We demonstrate the growth of dynamic connections among electrodes and surfactant droplets in reconfigurable setups─featuring a unique interplay between molecular assemblies and inorganic, solid structures.

A Versatile Synthesis Platform Based on Polymer Cubosomes for a Library of Highly Ordered Nanoporous Metal Oxides Particles.

Polymer cubosomes (PCs) have well-defined inverse bicontinuous cubic mesophases formed by amphiphilic block copolymer bilayers. The open hydrophilic channels, large periods, and robust physical properties of PCs are advantageous to many host-guest interactions and yet not fully exploited, especially in the fields of functional nanomaterials. Here, the self-assembly of poly(ethylene oxide)-block-polystyrene block copolymers is systematically investigated and a series of robust PCs is developed via a cosolvent method. Ordered nanoporous metal oxide particles are obtained by selectively filling the hydrophilic channels of PCs via an impregnation strategy, followed by a two-step thermal treatment. Based on this versatile PC platform, the general synthesis of a library of ordered porous particles with different pore structures , tunable large pore size (18-78nm), high specific surface areas (up to 123.3m2g-1 for WO3) and diverse framework compositions, such as transition and non-transition metal oxides, rare earth chloride oxides, perovskite, pyrochlore, and high-entropy metal oxides is demonstrated. As typical materials obtained via this method, ordered porous WO3 particles have the advantages of open continuous structure and semiconducting properties, thus showing superior gas sensing performances toward hydrogen sulfide.

Exosome Isolation Using Chitosan Oligosaccharide Lactate-1-Pyrenecarboxylic Acid-Based Self-Assembled Magnetic Nanoclusters.

Exosomes are small extracellular vesicles that play a crucial role in intercellular communication and offer significant potential for a wide range of biomedical applications. However, conventional methods for exosome isolation have limitations in terms of purity, scalability, and preservation of exosome structural integrity. To address these challenges, an exosome isolation platform using chitosan oligosaccharide lactate conjugated 1-pyrenecarboxylic acid (COL-Py) based self-assembled magnetic nanoclusters (CMNCs), is presented. CMNCs are characterized to optimize their size, stability, and interaction dynamics with exosomes. The efficiency of CMNCs in isolating exosomes is systematically evaluated using various analytical methods to demonstrate their ability to capture exosomes based on amphiphilic lipid bilayers. CMNC-based exosome isolation consistently yields exosomes with structural integrity and purity similar to those obtained using traditional methods. The reusability of CMNCs over multiple exosome isolation cycles underscores their scalability and offers an efficient solution for biomedical applications. These results are supported by western blot analysis, which demonstrated the superiority of CMNC-based isolation in terms of purity compared to conventional methods. By providing a scalable and efficient exosome isolation process that preserves both structural integrity and purity, CMNCs can constitute a new platform that can contribute to the field of exosome studies.

Molecular mechanism of decoupling between the fluorescence anisotropy thermograms of diphenylhexatriene and the thermotropic phase transitions of biomimetic ion pair amphiphile bilayers

The fluorescence anisotropy (FA) thermogram is a common technique to characterize the thermotropic phase properties and to determine the phase transition temperature of a lipid bilayer. For several biomimetic bilayer systems composed of ion pair amphiphiles (IPAs), however, the FA thermograms obtained with the 1,6-diphenyl-1,3,5-hexatriene (DPH) fluorescent probe fail to capture their phase transition behaviors. Here, we employed molecular dynamics (MD) simulation to examine the dynamics of common fluorescent probes, including DPH and 1-[4-(trimethylamino)phenyl]-6-phenyl-1,3,5-hexatriene (TMA-DPH), and evaluated the corresponding FA signals from the probe's rotational autocorrelation functions. The resulting FA thermogram of DPH in a DPPC bilayer indeed exhibits a sigmoidal feature that correlates with the phase behavior for the membrane. In contrast, the DPH FA thermogram fails to reflect the phase transition of IPA membranes with asymmetric or short alkyl tails. Such decoupling phenomenon is attributed to (1) the inherently disordered chain packing within the IPA bilayers of short alkyl tails, or (2) the flat orientation of DPH within the IPA bilayers featuring asymmetric alkyl chains. The FA thermograms further reweighted by the ratio of DPH flat orientation in IPA bilayers show excellent agreements with experimental data, demonstrating the importance of DPH orientation. Conversely, the amphiphilic TMA-DPH can capture the structural changes near the bilayer surface during the phase transition, applicable for a variety of IPA systems. The combined results provide important insights into the phase transition behaviors of different bilayer systems and offer guidance for probe selection in FA studies.

The Effect of Parent Cell Type on Small Extracellular Vesicle-Derived Vehicle Functionality.

Cell therapies involving c-kit+ progenitor cells (CPCs) and mesenchymal stem cells (MSCs) have been actively studied for cardiac repair. The benefits of such therapies have more recently been attributed to the release of small extracellular vesicles (sEVs) from the parent cells. These sEVs are 30-180nm vesicles containing protein/nucleic acid cargo encapsulated within an amphiphilic bilayer membrane. Despite their pro-reparative effects, sEV composition and cargo loading is highly variable, making it challenging to develop robust therapies with sEVs. Synthetic alternatives have been developed to allow cargo modulation, including prior work from the laboratory, to design sEV-like vehicles (ELVs). ELVs are synthesized from the sEV membrane but allow controlled cargo loading. It is previously shown that loading pro-angiogenic miR-126 into CPC-derived ELVs significantly increases endothelial cell angiogenesis compared to CPC-sEVs alone. Here, they expand on this work to design MSC-derived ELVs and study the role of the parent cell type on ELV composition and function. It is found that ELV origin does affect the ELV potency and that ELV membrane composition can affect outcomes. This study showcases the versatility of ELVs to be synthesized from different parent cells and highlights the importance of selecting ELV source cells based on the desired functional outcomes.

Antimicrobial peptides alter lipid bilayer properties before disrupting membrane barrier property.

Antimicrobial peptides (AMPs) have been the subject of inquiry since the initial search for antibiotics in the ­first half of 20th century; the first antibiotic used in humans was the linear pentadecapeptide gramicidin. Much of this interest comes from the modest frequency of bacterial resistance against AMPs. Though AMPs differ in sequence and structure, the majority share three core physicochemical properties; they are short, cationic and amphipathic. Moreover, enantiomers of AMPs tend to have similar potencies. These common features have led to a focus on the bacterial membrane as a target for AMPs. High concentrations of AMPs cause gross bilayer defects, through pore formation or micellar breakdown. At lower concentrations, AMPs have effects on bacterial physiology that appear unrelated to membrane permeabilization, suggesting that they may act through bilayer-mediated regulation (BMR) of membrane protein function. If correct, this offers a mechanism of action that integrates the known membrane-modifying effects of AMPs with their ability to broadly alter bacterial physiology at sub-pore forming concentrations. We tested this hypothesis using melittin, gramicidin S, and indolicidin, three AMPs with distinct structures, that indeed alter bilayer properties at concentrations below those required for pore formation. Contrary to expectation, AMP induced BMR is attenuated in anionic bilayers despite increased AMP binding, suggesting an organizing effect of membrane-bound counterions. We further found that amphiphilic bilayer modifiers promote membrane permeabilization, suggesting that BMR may be responsible for the cooperativity of AMP-induced permeabilization. Two membrane-impermeant detergents, CHAPS and zwittergent, promote pore formation despite inhibiting AMP binding, suggesting a role for leaflet-specific lateral pressure differences. These results suggest a new mechanism by which AMPs exert their bactericidal effect, which may guide antibiotic design and provide a path for circumventing bacterial resistance.

Polymersomes as virus-surrogate particles for evaluating the performance of air filter materials

The development of antivirus air filter materials has attracted considerable interests due to the pandemic of coronavirus disease 2019 (COVID-19). Filtration efficiency (FE) of these materials against virus is critical in the assessment of their use in disease prevention. Due to the high cost and biosafety laboratory required for conducting research using actual virus samples, surrogates for virus are commonly used in the filtration test. Here, we explore the employment of polymersomes (polymeric vesicles) as a new type of surrogate. The polymersomes are hollow shell nanoparticles with amphiphilic bilayer membranes, which can be fabricated in nanosized, and possess similar size and structural features to virus. The performance of commercial KN95 mask and surgical mask with micro-sized fibers, and electrospun polyvinylidene fluoride (PVDF) and polyacrylonitrile (PAN) nanofibers were chosen to be evaluated. The filtration tests against fluorescent-labeled virus-surrogate particles (VSPs), i.e. polymersomes, allowed the determination of the FE of the multilayered filter materials in a layer-specific manner. The results suggested the importance of hydrophobicity in designing the nanofibrous filter materials. The employment of VSPs in filtration performance evaluation allows a cost-effective way to estimate the FE against virus, providing guidance on future development of air filter materials.

Rheology of sliding leaflets in coarse-grained DSPC lipid bilayers.

Amphiphilic lipid bilayers modify the friction properties of the surfaces on top of which they are deposited. In particular, the measured sliding friction coefficient can be significantly reduced compared with the native surface. We investigate in this work the friction properties of a numerical coarse-grained model of DSPC (1,2-distearoyl-sn-glycero-3-phosphocholine) lipid bilayer subject to longitudinal shear. The interleaflet friction coefficient is obtained from out-of-equilibrium pulling or from relaxation simulations. In particular, we gain access to the transient viscoelastic response of a sheared bilayer. The bilayer mechanical response is found to depend significantly on the membrane physical state, with evidence in favor of a linear response regime in the fluid but not in the gel region. The linear response validity domain is established, and the timescales appearing in the membrane response discussed.

A Comprehensive Review on the Applications of Exosomes and Liposomes in Regenerative Medicine and Tissue Engineering

Tissue engineering and regenerative medicine are generally concerned with reconstructing cells, tissues, or organs to restore typical biological characteristics. Liposomes are round vesicles with a hydrophilic center and bilayers of amphiphiles which are the most influential family of nanomedicine. Liposomes have extensive research, engineering, and medicine uses, particularly in a drug delivery system, genes, and vaccines for treatments. Exosomes are extracellular vesicles (EVs) that carry various biomolecular cargos such as miRNA, mRNA, DNA, and proteins. As exosomal cargo changes with adjustments in parent cells and position, research of exosomal cargo constituents provides a rare chance for sicknesses prognosis and care. Exosomes have a more substantial degree of bioactivity and immunogenicity than liposomes as they are distinctly chiefly formed by cells, which improves their steadiness in the bloodstream, and enhances their absorption potential and medicinal effectiveness in vitro and in vivo. In this review, the crucial challenges of exosome and liposome science and their functions in disease improvement and therapeutic applications in tissue engineering and regenerative medicine strategies are prominently highlighted.

Manifolds of amphiphilic bilayers: Stability up to the boundary

We consider the mass preserving L 2 -gradient flow of the strong scaling of the functionalized Cahn Hilliard gradient flow and establish the nonlinear stability of a manifold comprised of quasi-equilibrium bilayer distributions up to the manifold's boundary. In the limit of thin but non-zero interfacial width, ε ≪ 1 , the bilayer manifold is parameterized by meandering modes that describe the interfacial evolution. The normal coercivity of the manifold is limited by “pearling” modes that control the structure of the profile near the interface, these are weakly damped and can lead to the dynamic rupture of the interface. Amphiphilic interfaces may decrease energy by either lengthening or shortening, depending upon the amphiphilic mass distributed in the bulk. We introduce an implicitly defined parameterization of the interfacial shape that uncouples the length change from the parameters describing the shape and introduce a nonlinear projection onto the manifold from a surrounding neighborhood. The bilayer manifold has asymptotically large but finite dimension tuned to maximize normal coercivity while preserving the wave-number gap between the meandering and the pearling modes. Modulo a pearling stability assumption, we show that the manifold attracts nearby orbits into a tubular neighborhood about itself so long as the interfacial shape remains sufficiently smooth and far from self-intersection. In a companion paper, [8] , we identify open sets of initial data whose orbits converge to circular equilibrium after a significant transient, and derive a singularly perturbed interfacial evolution comprised of motion against curvature regularized by an asymptotically weak Willmore term.

Bending elastic modulus of a polymer-doped lyotropic lamellar phase

The effect of inserting a neutral water-soluble adsorbing polymer on the flexibility of amphiphilic bilayers in a lamellar phase is investigated. The Lα system is a stack of charged undulating bilayers composed of sodium dodecyl sulfate (SDS) and octanol separated by aqueous solutions of polyethylene glycol (PEG). The mean bending elastic modulus κ is determined from the quadrupole splittings in the solid state NMR spectra of the perdeuterated octanol chains embedded in the membranes that undergo collective fluctuations. Parameters for describing the membrane behavior (bilayer thickness, elastic compressibility modulus, order parameter) are obtained by supplementing the NMR data with complementary experiments (x-ray scattering), NMR spectral simulations, and theoretical considerations. A fairly complete picture of the membrane rigidity emerges for any location in the lamellar phase thanks to a broad sweep of the lamellar domain by systematically varying the membrane fraction along dilution lines as well as the polymer composition. The most remarkable result is the difference between dilute and semi-dilute regimes. In the dilute PEG solution, no (or slight positive shift) polymer contribution to the rigidity curvature of the layered system is noted within the experimental resolution (≤0.3 kBT) and κ remains around 2.7 kBT. In contrast, the membrane rigidity increases steadily upon polymer addition once the crossover concentration cp* is exceeded, amounting to a 60% increase in κ at polymer concentration 2.5 cp* in the aqueous interlayers. These results are discussed with regard to the theoretical expectation of membrane rigidification upon irreversible polymer adsorption.

Atomistic Simulations on Interactions between Amphiphilic Janus Nanoparticles and Lipid Bilayers: Effects of Lipid Ordering and Leaflet Asymmetry.

Amphiphilic Janus nanoparticles, which are hydrophilic on one-half of the particle surface and hydrophobic on the other half, are ideal carrier candidates for drug delivery due to their unique physicochemical properties. In this study, we investigate the interactions between amphiphilic Janus nanoparticles coated with hydrophilic and hydrophobic ligands on each half of the surface of the nanoparticle and lipid bilayers with either symmetric or asymmetric leaflet structure and in different phases using atomistic molecular dynamics simulations. The results show that the Janus nanoparticle can easily insert into the liquid-disordered lipid bilayer and asymmetric lipid bilayers with the hydrophobic ligands inserted into the liquid-ordered leaflet. However, the nanoparticle barely inserts into the symmetric liquid-ordered lipid bilayer and tends to be adsorbed onto the surface of the liquid-ordered bilayers with the hydrophilic ligands contacting the surface of the bilayer. The insertion of the nanoparticle is mainly dominated by the hydrophobicity of the ligands, the lipid ordering, and the curvature of the bilayer. Rotation of the nanoparticle only occurs during the initial adsorption process of the nanoparticle onto the surface of the lipid bilayers. This work provides new insight into understanding the interactions of amphiphilic Janus nanoparticles with model biological membranes at the atomistic scale and the application of Janus nanoparticles for drug delivery.

Minimal Coarse-Grained Modeling toward Implicit Solvent Simulation of Generic Bolaamphiphiles.

A dual-site dimer model of bola or bipolar amphiphiles is developed based on an earlier single-site model of monopolar amphiphiles [Dey, S.; Saha, J. Phys. Rev. E 2017, 95, 023315]. This model incorporates both the hydrophobic effect and the hydration force in its anisotropic site-site interactions, thus obviating the need to simulate the water particles explicitly. Such economy of sites and absence of explicit solvents enable molecular dynamics simulations to achieve mesoscopic length and time scales unattainable by any bead-spring model or explicit solvent computations. Our model, however, applies to generic bolas only because the gain in scale can only be obtained by sacrificing the resolution of detailed molecular structures. Thanks to a pivoted dimer architecture, our model can incorporate the essential flexibility of bolas, which leads to their loop or U-shaped conformers. Rigid bolas can also be modeled by the same dimer simply by constraining the rotation about the pivot. Flexible model bolas show fast, spontaneous self-assembly into experimentally observed nanostructures such as micelles and rods. Tightly packed yet fluid monolayers can also be formed from these flexible dimers. Model bolalipids are seen to be less diffusive and produce thicker layers compared to their monopolar counterparts. Bilayers composed of monopolar model lipids show increased stability in the presence of membrane-spanning bolas. Rigid bolas, though achiral themselves, show self-assembly into helical rods. As all these observations agree with well-known characteristics of archaeal lipids and synthetic bolaamphiphiles, our model promises to be useful for mesoscale simulations of bolas in the context of research in lyotropic liquid crystals, biomimetics, drug delivery, and low-molecular-weight hydrogelators.

Pegylated Oleic Acid-Lecithin Liposomes (Poll) for Anticancer Drug Delivery

Cancer is a major health issue, conferring to more than 14.5 million deaths worldwide. Liposomes, self-assembly amphiphilic bilayer molecules, served as excellent alternative vehicles due to their ability to encapsulate both hydrophobic and hydrophilic anticancer drugs. Conventional liposomes, comprised mainly phospholipids are cost-ineffective, unstable, and easily degraded by the external environment. In this study, we introduced PEGylated oleic acid-lecithin liposomes constructed by using C-18 monounsaturated fatty acids (oleic acid) and soy lecithin, in the presence of DOPEPEG2000 in pH7.4, above their glass transition temperature, Tg, by employing the simple thin layer lipid hydration method. FTIR spectrum of oleic acid, soy lecithin, and DOPEPEG2000 was studied. The average particle size without further mechanical interference was 1102.3 nm while the zeta potential value was -18 mV, which is compatible with the zeta potential of the red blood cell. The polydispersity index (PDI) was reduced by 46.2% with the incorporation of the DOPEPEG2000. The morphological study using OPM showed the presence of spherical shape liposomes that exhibit the birefringence effect under the light field and Maltese cross under the dark field. Encapsulation of folinic acid, methotrexate, doxorubicin, or irinotecan resulted in greater than 75% encapsulation efficiency (EE). Half-maximal inhibitory concentration, IC50, was significantly reduced in POLL as compared to free anticancer drugs. Our data demonstrate POLL may be a promising alternative vehicle to deliver various anticancer drugs to targeted tumour sites.

Improved ordering and lubricating properties using graphene in lamellar liquid crystals of Triton X-100/CnmimNTf2/H2O.

Graphene has been studied extensively owing to its excellent lubricity performance. However, when used as lubricant additives, graphene layers tend to agglomerate and precipitate; further, poor dispersion will reduce the lubrication performance. Herein, graphene was evenly dispersed in Triton X-100/1-alkyl-3-methylimidazole ditrifluorosulfonylimide (CnmimNTf2)/H2O (n = 8, 12, and 16) lamellar liquid crystals (LLCs). The effects of the graphene concentration on the microstructures of the LLCs are detected by 2H NMR and small angle X-ray scattering measurements and their rheological and tribological performance are investigated in detail. The addition of 0.30 mg mL-1 graphene into the Triton X-100/C16mimNTf2/H2O LLC system led to a 15% reduction in the friction coefficient and 65% reduction in the wear volume when compared with the pure LLCs. The synergistic effect of the graphene and LLC hybrid system efficiently improved the lubrication performance, which is attributed to the higher order of the amphiphilic molecules and the thicker amphiphilic bilayer. The generated tribofilm formed by the physical adsorption and the tribochemical reaction of LLCs on the surface of steel is conducive to lubricity protection from abrasion. This study reveals that with the understanding of the microstructure change mechanism, the combination of graphene and LLCs could provide a new path to the design of a novel lubricant that can be utilized in nanostructures for energy saving applications.

Electrostatic shape control of a charged molecular membrane from ribbon to scroll

Bilayers of amphiphiles can organize into spherical vesicles, nanotubes, planar, undulating, and helical nanoribbons, and scroll-like cochleates. These bilayer-related architectures interconvert under suitable conditions. Here, a charged, chiral amphiphile (palmitoyl-lysine, C16-K1) is used to elucidate the pathway for planar nanoribbon to cochleate transition induced by salt (NaCl) concentration. In situ small- and wide-angle X-ray scattering (SAXS/WAXS), atomic force and cryogenic transmission electron microscopies (AFM and cryo-TEM) tracked these transformations over angstrom to micrometer length scales. AFM reveals that the large length (L) to width (W) ratio nanoribbons (L/W > 10) convert to sheets (L/W → 1) before rolling into cochleates. A theoretical model based on electrostatic and surface energies shows that the nanoribbons convert to sheets via a first-order transition, at a critical Debye length, with 2 shallow minima of the order of thermal energy at L/W >> 1 and at L/W = 1. SAXS shows that interbilayer spacing (D) in the cochleates scales linearly with the Debye length, and ranges from 13 to 35 nm for NaCl concentrations from 100 to 5 mM. Theoretical arguments that include electrostatic and elastic energies explain the membrane rolling and the bilayer separation-Debye length relationship. These models suggest that the salt-induced ribbon to cochleate transition should be common to all charged bilayers possessing an intrinsic curvature, which in the present case originates from molecular chirality. Our studies show how electrostatic interactions can be tuned to attain and control cochleate structures, which have potential for encapsulating, and releasing macromolecules in a size-selective manner.

Effects of Cholesterol on Water Permittivity of Biomimetic Ion Pair Amphiphile Bilayers: Interplay between Membrane Bending and Molecular Packing.

Ion pair amphiphile (IPA), a molecular complex composed of a pair of cationic and anionic amphiphiles, is an inexpensive phospholipid substitute to fabricate vesicles with various pharmaceutical applications. Modulating the physicochemical and permeation properties of IPA vesicles are important for carrier designs. Here, we applied molecular dynamics simulations to examine the cholesterol effects on the structures, mechanics, and water permittivity of hexadecyltrimethylammonium-dodecylsulfate (HTMA-DS) and dodecyltrimethylammonium- hexadecylsulfate (DTMA-HS) IPA bilayers. Structural and mechanical analyses indicate that both IPA systems are in gel phase at 298 K. Adding cholesterol induces alkyl chain ordering around the rigid sterol ring and increases the cavity density within the hydrophilic region of both IPA bilayers. Furthermore, the enhanced alkyl chain ordering and the membrane deformation energy induced by cholesterol increase the permeation free energy penalty. In contrast, cholesterol has minor effects on the water local diffusivities within IPA membranes. Overall, the cholesterol reduces the water permittivity of rigid IPA membranes due to the synergistic effects of increased alkyl chain ordering and enhanced membrane mechanical modulus. The results provide molecular insights into the effects of molecular packing and mechanical deformations on the water permittivity of biomimetic IPA membranes, which is critical for designing IPA vesicular carriers.

Microstructure and Tribological Properties of Lamellar Liquid Crystals Formed by Ionic Liquids as Cosurfactants.

Lamellar liquid crystals (LLCs) have been shown to have lubrication properties in many documents due to their bilayer structure. Ionic liquids are often used as additive or surfactant in LLCs. However, ionic liquids used as cosurfactants, which lead to a transition from the hexagonal liquid crystals to LLCs, are relatively rare. Herein, the microstructure of Triton X-100/C nmimNTf2/H2O LLCs formed by using 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquid (C nmimNTf2, n = 8, 12, 16) as cosurfactant has been determined by polarized light microscopy, small angle X-ray scattering, and 2H NMR technique, and their rheological and tribological properties were investigated. These LLCs show good friction-reducing and antiwear performances. The correlation between the microstructure of the LLCs and their lubricating mechanism is established. The increase of the concentration of C nmimNTf2 and the length of alkyl chain in the LLCs can lead to an obvious reduction in friction coefficients and wear volumes, which are attributed to the higher order of amphiphilic molecules, the thickness of the amphiphilic bilayer, and the smaller cross-sectional area of the polar head group at the hydrophilic and hydrophobic interfaces. The protective film formed by the physical adsorption of ionic liquid LLCs on the surface of friction disk pair and the tribochemical reaction has effectively promoted the lubrication effect. The good lubricating property and antiwear capability indicate their promising and potential applications in water lubrication and biological lubrication.