Block copolymer templated self-assembly of disk-shaped molecules.

Stacking of disk-shaped organic molecules is a promising strategy to develop electronic and photovoltaic devices. Here, we investigate the capability of a soft block copolymer matrix that microphase separates into a cylindrical phase to direct the self-assembly of disk-shaped molecules by means of molecular simulations. We show that two disk molecules confined in the cylinder domain experience a depletion force, induced by the polymer chains, which results in the formation of stacks of disks. This entropic interaction and the soft confinement provided by the matrix are both responsible for the structures that can be self-assembled, which include slanted or columnar stacks. In addition, we evidence the transmission of stresses between the different minority domains of the microphase, which results in the establishment of a long-ranged interaction between disk molecules embedded in different domains; this interaction is of the order of the microphase periodicity and may be exploited to direct assembly of disks at larger scales.

Elasticity-induced force reversal between active spinning particles in dense passive media.

The self-organization of active particles is governed by their dynamic effective interactions. Such interactions are controlled by the medium in which such active agents reside. Here we study the interactions between active agents in a dense non-active medium. Our system consists of actuated, spinning, active particles embedded in a dense monolayer of passive, or non-active, particles. We demonstrate that the presence of the passive monolayer alters markedly the properties of the system and results in a reversal of the forces between active spinning particles from repulsive to attractive. The origin of such reversal is due to the coupling between the active stresses and elasticity of the system. This discovery provides a mechanism for the interaction between active agents in complex and structured media, opening up opportunities to tune the interaction range and directionality via the mechanical properties of the medium.

Simulation methods for solvent vapor annealing of block copolymer thin films.

Recent progress in modelling the solvent vapor annealing of thin film block copolymers is examined in the context of a self-consistent field theory framework. Key control variables in determining the final microdomain morphologies include swelling ratio or swollen film solvent volume fraction, swollen film thickness, substrate and vapor atmosphere surface energies, effective volume fraction, and effective Flory-Huggins interaction parameter. The regime of solvent vapor annealing studied is where the block copolymer has a high enough Flory-Huggins parameter that ordered structures form during swelling and are then trapped in the system through quenching. Both implicit and explicit consideration of the solvent vapor is considered to distinguish the cases in which solvent vapor leads to a non-bulk morphology. Block-selective solvents are considered based on the experimental systems of polystyrene-b-polydimethylsiloxane annealed with toluene and heptane. The results of these simulations are compared with these experiments.

Templating three-dimensional self-assembled structures in bilayer block copolymer films.

The registration and alignment of a monolayer of microdomains in a self-assembled block copolymer thin film can be controlled by chemical or physical templating methods. Although planar patterns are useful for nanoscale device fabrication, three-dimensional multilevel structures are required for some applications. We found that a bilayer film of a cylindrical-morphology block copolymer, templated by an array of posts functionalized with a brush attractive to the majority block, can form a rich variety of three-dimensional structures consisting of cylinder arrays with controllable angles, bends, and junctions whose geometry is controlled by the template periodicity and arrangement. This technique allows control of microdomain patterns and the ability to route and connect microdomains in specific directions.

Conformational dynamics and internal friction in homopolymer globules: equilibrium vs. non-equilibrium simulations.

We study the conformational dynamics within homopolymer globules by solvent-implicit Brownian dynamics simulations. A strong dependence of the internal chain dynamics on the Lennard-Jones cohesion strength ε and the globule size N (G) is observed. We find two distinct dynamical regimes: a liquid-like regime (for ε < ε(s) with fast internal dynamics and a solid-like regime (for ε > ε(s) with slow internal dynamics. The cohesion strength ε(s) of this freezing transition depends on N (G) . Equilibrium simulations, where we investigate the diffusional chain dynamics within the globule, are compared with non-equilibrium simulations, where we unfold the globule by pulling the chain ends with prescribed velocity (encompassing low enough velocities so that the linear-response, viscous regime is reached). From both simulation protocols we derive the internal viscosity within the globule. In the liquid-like regime the internal friction increases continuously with ε and scales extensive in N (G) . This suggests an internal friction scenario where the entire chain (or an extensive fraction thereof) takes part in conformational reorganization of the globular structure.

Complex self-assembled patterns using sparse commensurate templates with locally varying motifs.

Templated self-assembly of block copolymer thin films can generate periodic arrays of microdomains within a sparse template, or complex patterns using 1:1 templates. However, arbitrary pattern generation directed by sparse templates remains elusive. Here, we show that an array of carefully spaced and shaped posts, prepared by electron-beam patterning of an inorganic resist, can be used to template complex patterns in a cylindrical-morphology block copolymer. We use two distinct methods: making the post spacing commensurate with the equilibrium periodicity of the polymer, which controls the orientation of the linear features, and making local changes to the shape or distribution of the posts, which direct the formation of bends, junctions and other aperiodic features in specific locations. The first of these methods permits linear patterns to be directed by a sparse template that occupies only a few percent of the area of the final self-assembled pattern, while the second method can be used to selectively and locally template complex linear patterns.

Multidimensional targeting: using physical and chemical forces in unison.

Targeted drug delivery has traditionally relied on finding highly specific biochemical markers at a target location. However, recent developments in this area have shown that purely physical and physicochemical factors are as important and can be used to aid in the targeting process. Here, we review the physicochemical factors affecting the targeting and delivery process and their relation to established biochemical markers. We refer to this combined approach as multidimensional targeting (MDT). More specifically, we examine the role of MDT factors across different length scales of relevance to the drug delivery pathway. Finally, we conclude with our perspective on the future of this burgeoning area.

Relaxation of ultralarge VWF bundles in a microfluidic-AFM hybrid reactor.

The crucial role of the biopolymer "Von Willebrand factor" (VWF) in blood platelet binding is tightly regulated by the shear forces to which the protein is exposed in the blood flow. Under high-shear conditions, VWFs ability to immobilize blood platelets is strongly increased due to a change in conformation which at sufficient concentration is accompanied by the formation of ultra large VWF bundles (ULVWF). However, little is known about the dynamic and mechanical properties of such bundles. Combining a surface acoustic wave (SAW) based microfluidic reactor with an atomic force microscope (AFM) we were able to study the relaxation of stretched VWF bundles formed by hydrodynamic stress. We found that the dynamical response of the network is well characterized by stretched exponentials, indicating that the relaxation process proceeds through hopping events between a multitude of minima. This finding is in accordance with current ideas of VWF self-association. The longest relaxation time does not show a clear dependence on the length of the bundle, and is dominated by the internal conformations and effective friction within the bundle.

Shear-induced unfolding triggers adhesion of von Willebrand factor fibers.

von Willebrand factor (VWF), a protein present in our circulatory system, is necessary to stop bleeding under high shear-stress conditions as found in small blood vessels. The results presented here help unravel how an increase in hydrodynamic shear stress activates VWF's adhesion potential, leading to the counterintuitive phenomena of enhanced adsorption rate under strong shear conditions. Using a microfluidic device, we were able to mimic a wide range of bloodflow conditions and directly visualize the conformational dynamics of this protein under shear flow. In particular, we find that VWF displays a reversible globule-stretch transition at a critical shear rate gamma(crit) in the absence of any adsorbing surface. Computer simulations reproduce this sharp transition and identify the large size of VWF's repeating units as one of the keys for this unique hydrodynamic activation. In the presence of an adsorbing collagen substrate, we find a large increase in the protein adsorption at the same critical shear rate, suggesting that the globule unfolding in bulk triggers the surface adsorption in the case of a collagen substrate, which provides a sufficient density of binding sites. Monitoring the adsorption process of multiple VWF fibers, we were able to follow the formation of an immobilized network that constitutes a "sticky" grid necessary for blood platelet adhesion under high shear flow. Because areas of high shear stress coincide with a higher chance for vessel wall damage by mechanical forces, we identified the shear-induced increase in the binding probability of VWF as an effective self-regulating repair mechanism of our microvascular system.

Shear-flow-induced unfolding of polymeric globules.

The behavior of a single collapsed polymer under shear flow is examined using hydrodynamic simulations and scaling arguments. Below a threshold shear rate gamma[.]{*}, the chain remains collapsed and only deforms slightly, while above gamma[.]{*} the globule exhibits unfolding/refolding cycles. Hydrodynamics are crucial: In the free draining case, gamma[.]{*} scales with the globule radius R as gamma[.]{*} approximately R{-1}, while in the presence of hydrodynamic interactions gamma[.]{*} approximately R. Experiments on the globular von Willebrand protein confirm the presence of an unfolding transition at a well-defined critical shear rate.