Calcium-triggered fusion of lipid membranes is enabled by amphiphilic nanoparticles.

Lipid membrane fusion is an essential process for a number of critical biological functions. The overall process is thermodynamically favorable but faces multiple kinetic barriers along the way. Inspired by nature's engineered proteins such as SNAP receptor [soluble N-ethylmale-imide-sensitive factor-attachment protein receptor (SNARE)] complexes or viral fusogenic proteins that actively promote the development of membrane proximity, nucleation of a stalk, and triggered expansion of the fusion pore, here we introduce a synthetic fusogen that can modulate membrane fusion and equivalently prime lipid membranes for calcium-triggered fusion. Our fusogen consists of a gold nanoparticle functionalized with an amphiphilic monolayer of alkanethiol ligands that had previously been shown to fuse with lipid bilayers. While previous efforts to develop synthetic fusogens have only replicated the initial steps of the fusion cascade, we use molecular simulations and complementary experimental techniques to demonstrate that these nanoparticles can induce the formation of a lipid stalk and also drive its expansion into a fusion pore upon the addition of excess calcium. These results have important implications in general understanding of stimuli-triggered fusion and the development of synthetic fusogens for biomedical applications.

Imparting Superhydrophobicity with a Hierarchical Block Copolymer Coating.

A robust and transparent silica-like coating that imparts superhydrophobicity to a surface through its hierarchical multilevel self-assembled structure is demonstrated. This approach involves iterative steps of spin-coating, annealing, and etching of polystyrene-block-polydimethylsiloxane block copolymer thin films to form a tailored multilayer nanoscale topographic pattern with a water contact angle up to 155°. A model based on the hierarchical topography is developed to calculate the wetting angle and optimize the superhydrophobicity, in agreement with the experimental trends, and explaining superhydrophobicity arising through the combination of roughness at different lengthscales. Additionally, the mechanical robustness and optically passive properties of the resulting hydrophobic surfaces are demonstrated.

Solvent-exposed lipid tail protrusions depend on lipid membrane composition and curvature.

The stochastic protrusion of hydrophobic lipid tails into solution, a subclass of hydrophobic membrane defects, has recently been shown to be a critical step in a number of biological processes like membrane fusion. Understanding the factors that govern the appearance of lipid tail protrusions is critical for identifying membrane features that affect the rate of fusion or other processes that depend on contact with solvent-exposed lipid tails. In this work, we utilize atomistic molecular dynamics simulations to characterize the likelihood of tail protrusions in phosphotidylcholine lipid bilayers of varying composition, curvature, and hydration. We distinguish two protrusion modes corresponding to atoms near the end of the lipid tail or near the glycerol group. Through potential of mean force calculations, we demonstrate that the thermodynamic cost for inducing a protrusion depends on tail saturation but is insensitive to other bilayer structural properties or hydration above a threshold value. Similarly, highly curved vesicles or micelles increase both the overall frequency of lipid tail protrusions as well as the preference for splay protrusions, both of which play an important role in driving membrane fusion. In multi-component bilayers, however, the incidence of protrusion events does not clearly depend on the mismatch between tail length or tail saturation of the constituent lipids. Together, these results provide significant physical insight into how system components might affect the appearance of protrusions in biological membranes, and help explain the roles of composition or curvature-modifying proteins in membrane fusion.

Origin of multiplexing capabilities of multifrequency magnetic ratchets.

Through a combination of theory, numerical simulation, and experiment, we investigate the motion of magnetic beads on the surface of a magnetic ratchet driven by multifrequency fields. Here, we focus on the influence of static forcing terms, which were not included in previous models, and we derive analytical models that show why the static forcing terms are responsible for inducing beads of two different sizes to move in opposite directions on the same ratchet potential. We begin our analysis with the simplest possible forcing model, and we show that the main effect of the static forcing terms is to delay the phase of flux reversal. From there, we move onto the full analysis and theoretically derive the phase range for which opposite motion among two different bead types is achieved. Based on these theoretical results, we conduct experimental investigations that explore the effects of bead size and static forcing coefficient on the direction of bead motion, which confirm most of the expected trends. These results shed light both on past experimental work both by ourselves and others, as well as elucidate the more general multiplexing capabilities of ratchets.

Binary colloidal structures assembled through Ising interactions.

New methods for inducing microscopic particles to assemble into useful macroscopic structures could open pathways for fabricating complex materials that cannot be produced by lithographic methods. Here we demonstrate a colloidal assembly technique that uses two parameters to tune the assembly of over 20 different pre-programmed structures, including kagome, honeycomb and square lattices, as well as various chain and ring configurations. We programme the assembled structures by controlling the relative concentrations and interaction strengths between spherical magnetic and non-magnetic beads, which behave as paramagnetic or diamagnetic dipoles when immersed in a ferrofluid. A comparison of our experimental observations with potential energy calculations suggests that the lowest energy configuration within binary mixtures is determined entirely by the relative dipole strengths and their relative concentrations.

Dynamic electrostatic lithography: multiscale on-demand patterning on large-area curved surfaces.

Dynamic electrostatic lithography is invented to dynamically generate various patterns on large-area and curved polymer surfaces under the control of electrical voltages. The shape of the pattern can be tuned from random creases and craters to aligned creases, craters and lines, and the size of the pattern from millimeters to sub-micrometers.

Multiplexing superparamagnetic beads driven by multi-frequency ratchets.

Here, we explore the single particle dynamics of superparamagnetic beads exposed to multifrequency ratchets. Through a combination of theory, simulation, and experiment, we determine the important tuning parameters that can be used to implement multiplexed separation of polydisperse colloidal mixtures. In particular, our results demonstrate that the ratio of driving frequencies controls the transition between open and closed trajectories that allow particles to be transported across a substrate. We also demonstrate that the phase difference between the two frequencies controls not only the direction of motion but also which particles are allowed to move within a polydisperse mixture. These results represent a fundamentally different approach to colloidal separation than the previous methods which are based on controlling transitions between phase-locked and phase-slipping regimes, and have a higher degree of multiplexing capabilities that can benefit the fields of biological separation and sensing as well as provide crucial insights into general ratchet behavior.

Transport of superparamagnetic beads through a two-dimensional potential energy landscape.

The nonlinear dynamic behavior of superparamagnetic beads transported through a two-dimensional potential energy landscape is explored empirically and through numerical simulation. The beads are driven through a periodic array of micromagnets by an external rotating field oriented at an angle θ relative to the magnetization direction of the substrate. The bead's motion was highly sensitive to the angle of the driving field near critical angles and to various system parameters, including bead size, rotation frequency, and substrate pole density. Our results suggest the possibility of using this behavior in a highly discriminative colloidal separation system, in which two different bead types can be tuned to move in orthogonal directions.