Instability of membranes containing ionizable cationic lipids: Effects of the repulsive range of headgroups and tail structures.

The stability of membranes formed by ionizable cationic lipids, which constitute the primary components in lipid nanoparticles capable of endosomal escape, is explored using coarse-grained dissipative particle dynamics. Three types of ionizable model lipids with different tail structures are considered. Endosome acidification causes the ionization of lipids, leading to an increased repulsive range between their headgroups. When electrostatic repulsion is modeled as a conservative force with a long-range cutoff distance (rc,HH), the membrane and vesicle experience a loss of structural integrity and develop holes as rc,HH is beyond a critical value, which varies with the tail structure. When Coulombic repulsion is explicitly incorporated and intensified, a fully ionized lipid membrane undergoes a loss of structural integrity, displaying a qualitative similarity to the effect observed with the increase in rc,HH on the membrane stability. Qualitatively similar results are obtained for partially ionized membranes as the fraction of charged lipids increases. The stability of a mixed lipid membrane containing both ionizable and conventional lipids is also investigated. The disruption of the bilayer structure occurs for a sufficiently high charged fraction. The membrane instability can be attributed to the decrease in the packing parameter, which significantly deviates from unity as the interaction range increases.

One-step Fabrication of Physical Eutectogel with Recyclability: Crystalline Domain Regulation Induced by Microgels.

HYPOTHESIS: Despite their non-volatility, low cost, and recyclability, physical eutectogels' appeal is hindered by the intricate fabrication process and the involvement of hazardous chemicals. The network of polyvinyl alcohol (PVA) in deep eutectic solvent (choline chloride and glycerol) might be developed by the addition of microgels of polyacrylic acid (Carbopol). EXPERIMENTS: Hydrogen-bond interactions between Carbopol and PVA are revealed through Fourier-transform infrared spectroscopy. The impact of microgels on crystalline domains and the polymer network can be observed using X-ray diffraction and scanning electron microscopy. The physical properties of the eutectogel, including mechanical strength and ionic conductivity, are investigated as well. Finally, the strain-sensing ability and remarkable recyclability of the eutectogel are demonstrated. FINDINGS: The physical eutectogel can be obtained through a one-step fabrication process using only green and low-cost materials. It demonstrates robust strength (1.02 MPa) and remarkable stretchability (1000 % strain). This is attributed to the uniform dispersion of PVA crystalline domains within the deep eutectic solvent, facilitated by the hydrogen bonds and space restriction effects between PVA and Carbopol. Furthermore, the physical eutectogel with recyclability can consistently generate electrical resistance signals, highlighting its potential as a reliable strain sensor.

Ag NPs-coated polyurethane sponge as a water filter for removal of toxic metal ions at high concentrations.

Heavy metal ions are toxic to humans, plants, and marine life, making it crucial to eliminate them from water. This study reports the development of a new nanocomposite material (Alg@Ag/PU) that involves modifying silver nanoparticles (Ag NPs) with alginate (Alg) and coating them onto a polyurethane sponge (PU) for removing heavy metal ions. The successful coating of Alg@Ag NPs onto PU due to their strong chemical binding was confirmed by morphology and size characterization. Batch experiments were conducted to evaluate the removal efficiency of heavy metal ions at high concentrations (∼100 mg/L). The maximum adsorption amount was achieved within 6 h, and the highest removal efficiency was obtained at pH values between 6 and 7. Furthermore, the Alg@Ag/PU nanocomposite demonstrated excellent recyclability for metal ion removal even after 5 cycles. In summary, this work developed a simple and cost-effective method for producing an environmentally-friendly nanocomposite material for the efficient removal of heavy metal ions.

Imbibition Dynamics in a U-Groove Microchannel with Sudden Enlargement.

Imbibition dynamics in a rectangular U-groove that is connected to a sudden enlargement and complicated by the presence of Concus-Finn (CF) filaments is investigated using many-body dissipative particle dynamics. For open-ended sudden enlargement, four flow types are identified and depend on the contact angle θy, the critical angle θf associated with the occurrence of CF filaments, and the critical angle θc associated with the occurrence of main flow. First, for θy > θf and θy > θc, the corner flow is absent, and the main flow stops at the end of the small U-groove. Second, for θc > θy > θf, the corner flow vanishes, but the main flow occurs. Third, for θf > θy > θc, the corner flow takes place in the large U-groove, but the main flow is still absent. Fourth, for θy < θf and θy < θc, both the corner and main flows appear in the large U-groove. Additionally, the flow dynamics is greatly influenced by the length of the large U-groove (le). For closed-ended sudden enlargement, similar findings can be obtained. However, the outcome of the third case is altered for sufficiently small le, and the sudden enlargement can eventually be filled.

Jammed Microgels in Deep Eutectic Solvents as a Green and Low-Cost Ink for 3D Printing of Reliable Auxetic Strain Sensors.

Additive manufacturing is a promising technique for offering novel functionality to various materials by creating three-dimensional (3D) structures. However, the development of sustainable synthesis processes for 3D printing inks or 3D-printed materials remains a major challenge. In this work, a simple two-step mixing approach is developed to prepare a 3D printing ink from green, low-cost, and low-toxicity materials [commercial Carbopol and deep eutectic solvents (DESs)]. A small weight fraction of Carbopol can impart desired rheological properties to the DES used in the 3D printing ink and also can significantly enhance the stretchability of eutectogels up to 2500% strain. The 3D-printed auxetic structure shows a negative Poisson's ratio (within 100% strain), high stretchability (300%), high sensitivity (gauge factor of 3.1), good moisture resistance, and sufficient transparency. It can detect human motion with high skin comfort and breathability. The results of this work highlight a green, low-cost, and energy-saving strategy to fabricate conductive microgel-based inks for 3D printing of wearable devices.

Microstructural Dynamics of Polymer Melts during Stretching: Radial Size Distribution.

The transient elongational viscosity ηe(t) of the polymer melt is known to exhibit strain hardening, which depends on the strain rate ε˙. This phenomenon was elucidated by the difference of chain stretching in the entanglement network between extension and shear. However, to date, the microscopic evolution of polymer melt has not been fully statistically analyzed. In this work, the radial size distributions P(Rg,t) of linear polymers are explored by dissipative particle dynamics during the stretching processes. In uniaxial extensional flow, it is observed that the mean radius of gyration R¯g(t) and standard deviation σ(t) remain unchanged until the onset of strain hardening, corresponding to linear viscoelasticity. Both R¯g and σ rise rapidly in the non-linear regime, and bimodal size distribution can emerge. Moreover, the onset of strain hardening is found to be insensitive to the Hencky strain (ε˙Ht) and chain length (N).

Atypical vesicles and membranes with monolayer and multilayer structures formed by graft copolymers with diblock side-chains: nonlamellar structures and curvature-enhanced permeability.

Graft copolymers with diblock side-chains Am(-graft-B3Ay)n in a selective solvent have been reported to self-assemble into vesicles, but the structure is expected to differ distinctly from those of lipid bilayers. Surprisingly, the number of alternating hydrophobic A-block and hydrophilic B-block layers in the vesicle can vary from a monolayer to multilayers such as the hepta-layer, subject to the same copolymer concentration. The area density of the copolymer layer is not uniform across the membrane. This structural difference among different layers is attributed to the neighboring environment and the curvature of the layer. Because of the unusual polymer conformations, nonlamellar structures of polymersomes are formed, and they are much more intricate than those of liposomes. In fact, a copolymer can contribute to a single or two hydrophilic layers, and it can provide up to three hydrophobic layers. The influence of the backbone length (m) and side-chain length (y) and the permeation dynamics are also studied. The thickness of hydrophobic layers is found to increase with increasing side-chain length but is not sensitive to the backbone length. Although the permeation time increases with the layer number for planar membranes, the opposite behavior is observed for spherical vesicles owing to the curvature-enhanced permeability associated with Laplace pressure.

Interfacial assembly of nanorods: smectic alignment and multilayer stacking.

Large-scale spatial arrangement and orientation ordering of nanorod assembly on substrates are critical for nanodevice fabrication. However, complicated processes and templates or surface modification of nanorods are often required. In this work, we demonstrate, by dissipative particle dynamics simulations, that various ordered structures of adsorbed nanorods on smooth substrates can be simply achieved by non-affinity adsorption. The structures of interfacial assembly, including monolayers with a nematic-like arrangement and multilayer stacking with a smectic-like arrangement, depend on the nanorod concentration and the solvent size. As the nanorod concentration increases, the adsorbed layer becomes densely packed and the arrangement of nanorods changes from nematic-like to smectic. The assembly process driven by entropy is a two-dimensional layer-by-layer growth. Multilayer stacking with a smectic-like arrangement takes place at dilute concentrations of nanorods for large solvents such as pentamers, but at concentrated concentrations, it takes place for small solvents such as monomers. Moreover, nanorod bundles appear in the bulk phase for large solvents at dilute concentrations. The proposed strategy for interfacial assembly is caused by the free volume released for solvents, which is independent of the chemical compositions of substrates and nanorods.

Thermally assisted mobility of nanodroplets on surfaces with weak defects.

HYPOTHESIS: Thermal activation plays an essential role in contact line dynamics on nanorough surfaces. However, the relation between the aforementioned concept and the sliding motion of nanodroplets remains unclear. As a result, thermally assisted motion of nanodroplets on nanorough surfaces is investigated in this work. EXPERIMENTS: Steady slide and random motion of nanodroplets on surfaces with weak defects are investigated by Many-body Dissipative Particle Dynamics. The surface roughness is characterized by the slip length acquired from the velocity profile associated with the flowing film. FINDINGS: The slip length is found to decline with increasing the defect density. The linear relationship between the sliding velocity and driving force gives the mobility and reveals the absence of contact line pinning. On the basis of the Navier condition, a simple relation is derived and states that the mobility is proportional to the slip length and the reciprocal of the product of viscosity and contact area. Our simulation results agree excellently with the theoretical prediction. In the absence of external forces, a two-dimensional Brownian motion of nanodroplets is observed and its mean square displacement decreases with increasing the defect density. The diffusivity is proportional to the mobility, consistent with the Einstein relation. This consequence suggests that thermal fluctuations are able to overcome contact line pinning caused by weak defects.

Preferred penetration of active nano-rods into narrow channels and their clustering.

In a channel connected to a reservoir, passive particles prefer staying in the reservoir than the channel due to the entropic effect, as the size of the particles is comparable to that of the channel. Self-propelled rods can exhibit out-of-equilibrium phenomena, and their partition behavior may differ from that of passive rods due to their persistent swimming ability. In this work, the distribution of active nano-rods between the nanoscale channel and reservoir is explored using dissipative particle dynamics. The ratio of the nano-rod concentration in the slit to that in the reservoir, defined as the partition ratio Ψ, is a function of active force, channel width, and rod length. Although passive nano-rods prefer staying in bulk (Ψ < 1), active rods can overcome the entropic barrier and show favorable partition toward narrow channels (Ψ > 1). As the slit width decreases to about the rod's width, active rods entering the slit behave like a quasi-two-dimensional system dynamically. At sufficiently high concentrations and Peclet numbers, nano-rods tend to align and move together in the same direction for a certain time. The distribution (PM) of the cluster size (M) follows a power law, PM ∝ M-2, for small clusters.

Strengthening mechanism of the mechanical properties of graft copolymers with incompatible pendant groups: nano-clusters and weak cross-linking.

It is known that the adhesive property and mechanical strength of an apolar polymer can be improved by grafting with polar side chains, whereas the underlying mechanism is still elusive. In this work, the equilibrium structure and mechanical moduli of the melt of graft copolymers have been explored by dissipative particle dynamics. Due to the strong immiscibility of the non-polar backbone and polar side chains, nano-clusters of side chains formed and acted as physical crosslinkers. Moreover, non-affinity adsorption of polar side chains in the melt to the wall was observed, revealing an improvement in the adhesion property. Subjecting graft copolymers to cyclic deformation, the storage and loss moduli were acquired, and they grew with increasing grafting density. The melt strength in terms of the crossover frequency ascended with more side chains on the backbone. Our findings reveal that the strengthening of the mechanical properties of graft copolymers can be attributed to the formation of weakly cross-linked structures, thus offering an insight into the molecular design to aid the development of stronger graft copolymers.

Non-affinity adsorption of nanorods onto smooth walls via an entropy driven mechanism.

Preferential adsorption of nanorods onto smooth walls is investigated using dissipative particle dynamics in the absence of specific attraction and a depletant. Although the translational and rotational entropy of nanorods is significantly reduced after adsorption, the effective attraction between the nanorod and wall is clearly identified based on the distribution profile of rods. As the rod length increases, the attractive interaction grows stronger and clusters of aligned nanorods can emerge on the smooth wall. However, the presence of a depletion zone of nanorods adjacent to the adsorbed layer gives zero surface excess. These two regions correspond to the primary minimum and maximum mean force potentials observed. Since adsorbed nanorods lose their rotational and translational entropy, the strong adsorption of long nanorods has to be attributed to the entropy gain associated with the increase in free volume for the solvent in this athermal system. Nonetheless, as the surface roughness is present, entropy-driven attraction is lessened, similar to the depletion force between colloids.

Floating and Diving Loops of ABA Triblock Copolymers in Lipid Bilayers and Stability Enhancement for Asymmetric Membranes.

Hybrid membranes of lipids and AxByAz triblock copolymers can possess better biocompatibility and mechanical stability. In this work, triblock copolymer conformations and stability of asymmetric membranes are explored by dissipative particle dynamics. The triblock copolymers in the membranes exhibit either the bridge or loop conformation. As hydrophobic B-blocks interact attractively with lipid heads, bridge-shaped copolymers are significantly inhibited and loop-shaped copolymers prefer to stay at the interface between hydrophilic and hydrophobic layers. This floating loop has a flattened conformation, consistent with the experimental findings. In contrast, for repulsive interactions between B-blocks and lipid heads, bridge-shaped copolymers are abundant and loop-shaped copolymers tend to plunge into the hydrophobic layer. This diving loop displays a random coil conformation. The asymmetric membrane in which the fractions of loop-shaped copolymers in the upper and lower leaflets are different is thermodynamically unstable. Two approaches are proposed to acquire kinetically stable asymmetric membranes. First, membrane symmetrization is arrested by eliminating bridge-shaped copolymers, which is achieved by B-block/lipid head attraction and B-block/lipid tail repulsion. Second, asymmetric triblock copolymers (x ≠ z) are used to prevent the passage of the long A-block through the hydrophobic layer.

Directed self-propulsion of droplets on surfaces absent of gradients for cargo transport.

HYPOTHESIS: Manipulating droplet transportation without inputting work is desired and important in microfluidic systems. Although the creation of wettability gradient on surfaces has been employed to achieve this goal, the transport distance is very limited, hindering its applications in long-term operations. EXPERIMENTS: Here, we show that programming long-ranged transport of droplets on surfaces can be achieved by the addition of trisiloxane surfactants and the creation of deep grooves. The former provides Marangoni stress to actuate the droplet motion and also reduces the inherent contact line pinning. The latter acts as a railing to guide the motion of surfactant-laden droplets to follow various layouts with geometric features of roads. FINDINGS: It is found that the droplets with microliters can move over 20 cm. This work-free method is applicable to a variety of substrate materials and liquids. By using self-running shuttles, a convenient platform for liquid cargos transport is developed and demonstrated. Moreover, the coalescence of cargos carried by different shuttles is accomplished in a three-branch layout, revealing new droplet microreactors.

Size-dependence and interfacial segregation in nanofilms and nanodroplets of homologous polymer blends.

The size-dependent behavior of nanofilms and nanodroplets of homologous polymer blends was explored by many-body dissipative particle dynamics. Although a homologous blend can be regarded as a completely miscible and athermal system, enrichment of the surface in short polymers always takes place. First, liquid-gas and solid-liquid interfacial tensions of polymer melts were acquired. It is found that they increase and approach asymptotes with increasing chain lengths. The molecular weight dependence can be depicted using two semi-empirical expressions. Second, the variation of surface tension and surface excess of polymer blend nanofilms with the thickness was observed. Surface tension of the blend is observed to increase but the extent of surface segregation decreases upon increasing the film thickness. Finally, the wetting phenomenon of nanodroplets of homologous blends was examined. The contact angle is found to increase as the droplet size is reduced. Our simulation results indicate that the size-dependence of nanofilms and nanodroplets is closely related to surface segregation in homologous blends.

Size-dependent behavior and failure of young's equation for wetting of two-component nanodroplets.

HYPOTHESIS: For macroscopic systems, the interfacial properties are size-independent and Young's equation is generally valid for smooth substrates. For nanoscale systems, however, size-dependence and failure of Young's equation may emerge. EXPERIMENTS: The wetting behavior of a nanodroplet containing two miscible liquids on a smooth substrate is explored by many-body dissipative particle dynamics simulations. The size-dependent surface tension of nanofilms is investigated as well. FINDINGS: It is found that Young's equation is valid for nanodroplets of pure fluids but fails for two-component nanodroplets. The actual contact angle is always larger than the Young's contact angle, and their difference is getting smaller as the composition approaches pure fluids or the compatibility of the mixture is increased. The failure of Young's equation is closely associated with the size-dependent behavior in two-component nanodroplets and nanofilms. As the nanodroplet size is increased, the actual contact angle is found to decline but approaches a constant expected in macroscopic systems. Similarly, as the nanofilm thickness is increased, surface tension decreases and reaches its macroscopic value. The change of surface tension is attributed to the size-dependent surface composition, which is responsible for the failure of Young's equation.

UV-Resistant Self-Healing Emulsion Glass as a New Liquid-like Solid Material for 3D Printing.

Directly writing 3D structures into supporting mediums is a relatively new developing technology in additive manufacturing. In this work, durable and recyclable liquid-like solid (LLS) materials are developed as supporting mediums that are stable for both UV and thermal solidification. Our LLS material is comprised of densely packed oil droplets in a continuous aqueous medium, known as emulsion glass. Its elastic nature emerges from the jammed structure of oil droplets, which offers this LLS material rapidly self-healing ability. Moreover, the yield stress of the glass is relatively low and can be tuned by the viscosity and weight percentage of oil. The capability of the emulsion glass as supporting mediums is successfully demonstrated by directly writing and then curing designed structures. The emulsion glass has been repeatedly used at least 6 times upon exposure to UV irradiation and heat, implying it can expand the applications of supporting medium to the writing process involving UV- and thermal-curable inks simultaneously.