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

The Statistical Mechanics of Dynamic Pathways to Self-assembly

We describe some of the important physical characteristics of the `pathways', i.e. dynamical processes, by which molecular, nanoscale and micron-scale self-assembly occurs. We highlight the fact that there exist features of self-assembly pathways that are common to a wide range of physical systems, even though those systems may be different in respect of their microscopic details. We summarize some existing theoretical descriptions of self-assembly pathways, and highlight areas -- notably, the description of self-assembly pathways that occur `far' from equilibrium -- that are likely to become increasingly important.Comment: To appear in Annual Review of Physical Chemistr

Intrinsic Universality in Self-Assembly

We show that the Tile Assembly Model exhibits a strong notion of universality where the goal is to give a single tile assembly system that simulates the behavior of any other tile assembly system. We give a tile assembly system that is capable of simulating a very wide class of tile systems, including itself. Specifically, we give a tile set that simulates the assembly of any tile assembly system in a class of systems that we call \emph{locally consistent}: each tile binds with exactly the strength needed to stay attached, and that there are no glue mismatches between tiles in any produced assembly. Our construction is reminiscent of the studies of \emph{intrinsic universality} of cellular automata by Ollinger and others, in the sense that our simulation of a tile system $T$ by a tile system $U$ represents each tile in an assembly produced by $T$ by a $c \times c$ block of tiles in $U$, where $c$ is a constant depending on $T$ but not on the size of the assembly $T$ produces (which may in fact be infinite). Also, our construction improves on earlier simulations of tile assembly systems by other tile assembly systems (in particular, those of Soloveichik and Winfree, and of Demaine et al.) in that we simulate the actual process of self-assembly, not just the end result, as in Soloveichik and Winfree's construction, and we do not discriminate against infinite structures. Both previous results simulate only temperature 1 systems, whereas our construction simulates tile assembly systems operating at temperature 2

DNA Computing by Self-Assembly

Information and algorithms appear to be central to biological organization and processes, from the storage and reproduction of genetic information to the control of developmental processes to the sophisticated computations performed by the nervous system. Much as human technology uses electronic microprocessors to control electromechanical devices, biological organisms use biochemical circuits to control molecular and chemical events. The engineering and programming of biochemical circuits, in vivo and in vitro, would transform industries that use chemical and nanostructured materials. Although the construction of biochemical circuits has been explored theoretically since the birth of molecular biology, our practical experience with the capabilities and possible programming of biochemical algorithms is still very young

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