Self-assembly and dis-assembly of stimuli responsive tadpole-like single chain nanoparticles using a switchable hydrophilic/hydrophobic boronic acid cross-linker

Living systems are driven by molecular machines that are composed of folded polypeptide chains, which are assembled together to form multimeric complexes. Although replicating this type of system is a longstanding goal in polymer science, the complexity the structures impose is synthetically very challenging, and generating synthetic polymers to mimic the process of these assemblies appears to be a more appealing approach. To this end, we report a linear polymer programmable for stepwise folding and assembly to higher order structures. To achieve this, a diblock copolymer composed of 4-acryloylmorpholine and glycerol acrylate was synthesised with high precision via reversible addition fragmentation chain transfer polymerisation (Đ < 1.22). Both intramolecular folding and intermolecular assembly were driven by a pH responsive cross-linker, benzene-1,4-diboronic acid. The resulting intramolecular folded single chain nanoparticles were well defined (Đ < 1.16) and successfully assembled into a multimeric structure (Dh = 245 nm) at neutral pH with no chain entanglement. The assembled multimer was observed with a spherical morphology as confirmed by TEM and AFM. These structures were capable of unfolding and disassembling either at low pH or in the presence of sugar. This work offers a new perspective for the generation of adaptive smart materials

Fuel Efficient Computation in Passive Self-Assembly

In this paper we show that passive self-assembly in the context of the tile self-assembly model is capable of performing fuel efficient, universal computation. The tile self-assembly model is a premiere model of self-assembly in which particles are modeled by four-sided squares with glue types assigned to each tile edge. The assembly process is driven by positive and negative force interactions between glue types, allowing for tile assemblies floating in the plane to combine and break apart over time. We refer to this type of assembly model as passive in that the constituent parts remain unchanged throughout the assembly process regardless of their interactions. A computationally universal system is said to be fuel efficient if the number of tiles used up per computation step is bounded by a constant. Work within this model has shown how fuel guzzling tile systems can perform universal computation with only positive strength glue interactions. Recent work has introduced space-efficient, fuel-guzzling universal computation with the addition of negative glue interactions and the use of a powerful non-diagonal class of glue interactions. Other recent work has shown how to achieve fuel efficient computation within active tile self-assembly. In this paper we utilize negative interactions in the tile self-assembly model to achieve the first computationally universal passive tile self-assembly system that is both space and fuel-efficient. In addition, we achieve this result using a limited diagonal class of glue interactions

Approximate Self-Assembly of the Sierpinski Triangle

The Tile Assembly Model is a Turing universal model that Winfree introduced in order to study the nanoscale self-assembly of complex (typically aperiodic) DNA crystals. Winfree exhibited a self-assembly that tiles the first quadrant of the Cartesian plane with specially labeled tiles appearing at exactly the positions of points in the Sierpinski triangle. More recently, Lathrop, Lutz, and Summers proved that the Sierpinski triangle cannot self-assemble in the "strict" sense in which tiles are not allowed to appear at positions outside the target structure. Here we investigate the strict self-assembly of sets that approximate the Sierpinski triangle. We show that every set that does strictly self-assemble disagrees with the Sierpinski triangle on a set with fractal dimension at least that of the Sierpinski triangle (roughly 1.585), and that no subset of the Sierpinski triangle with fractal dimension greater than 1 strictly self-assembles. We show that our bounds are tight, even when restricted to supersets of the Sierpinski triangle, by presenting a strict self-assembly that adds communication fibers to the fractal structure without disturbing it. To verify this strict self-assembly we develop a generalization of the local determinism method of Soloveichik and Winfree

Self-adjusting assembly jig

Jig adjusts for thermal expansion and contraction to hold parts being joined under constant pressure and in correct alignment during entire joining operation. Jig is simple and easy to use, durable and maintenance free. Several methods may be used to join parts of many sizes and shapes

Biocatalytic self-assembly cascades

The properties of supramolecular materials are dictated by both kinetic and thermodynamic aspects, providing opportunities to dynamically regulate morphology and function. Herein, we demonstrate time-dependent regulation of supramolecular self-assembly by connected, kinetically competing enzymatic reactions. Starting from Fmoc-tyrosine phosphate and phenylalanine amide in the presence of an amidase and phosphatase, four distinct self-assembling molecules may be formed which each give rise to distinct morphologies (spheres, fibers, tubes/tapes and sheets). By varying the sequence or ratio in which the enzymes are added to mixtures of precursors, these structures can be (transiently) accessed and interconverted. The approach provides insights into dynamic self-assembly using competing pathways that may aid the design of soft nanostructures with tunable dynamic properties and life times