Nature offers a remarkable diversity of nanomaterials that have extraordinary functional and structural properties. Intrinsic to nature is the impressive ability to form complex ordered nanomaterials via self-organization. One particularly intriguing nanostructure is the gyroid, a network-like structure exhibiting high symmetry and complex topology. Although its existence in cells and tissues across many biological kingdoms is well documented, how and why it forms remains elusive and uncovering these formation mechanisms will undoubtedly inform bioinspired designs. A beautiful example is the smooth single gyroid that is found in the wing scales of several butterflies, where it behaves as a photonic crystal generating a vibrant green color. Here, we report that the gyroid structures of the Emerald-patched Cattleheart, Parides sesostris, develop as woven fibrillar structures, in contrast to the commonly held assumption that they form as smooth constructs. Ultramicroscopy of pupal tissue reveals that the gyroid geometry consists of helical weavings of fibers, akin to hyperbolic line patterns decorating the gyroid. Interestingly, despite their fibrillar nature, electron diffraction reveals the absence of crystalline order within this material. Similar fibrillar structures are also observed in the mature wing scales of P. sesostris specimens with surgically altered pupal development, leading to a blue coloration. Our findings not only introduce a variation of the gyroid in biology but also have significant implications for our understanding of its formation in nature.
Star-polyphiles are generalizations of lipids or surfactants [1]: they are small molecules consisting of 3 mutually immiscible chains attached to a common center: a hydrocarbon, a fluorocarbon and a water soluble oligo-ethylene glycol chain [2,3].When brought in contact with water, these selfassemble into mesophases, most of which structurally resemble those found in lipids like monoolein, including lamellar, hexagonal, micellar and bicontinuous cubic mesophases.However, the hydrophobic membrane is split into separate hydrocarbon and fluorocarbon domains [4], which significantly increases structural complexity and hierarchical ordering can occur.Here we give an overview on possible and experimentally determined mesophase geometries, focusing on their experimental investigation by SAXS and SANS in combination with scattering simulations of model structures.Figure 1.Gyroid mesophase based on star-polyphiles with de-mixed hydrocarbon-fluorocarbon domains schematically drawn in the form of stripes.In a binary star-polyphile/water system the demixed domain widths are limited by the geometry of the molecules (A).De-mixed domain widths can be enlarged by replacing part of the star-polyphile with the corresponding double-chain molecules (B)
Self-assembly is the process by which individual components arrange themselves into an ordered structure by changing the shapes, components, and interactions. It has enabled us to construct an extensive range of geometric forms on many length scales. Nevertheless, the potential of two-dimensional polygonal nanoplates to self-assemble into extended three-dimensional structures with compartments and corridors has remained unexplored. In this paper, we show coarse-grained Monte Carlo simulations demonstrating self-assembly of hexagonal/triangular nanoplates via complementary interactions into faceted, sponge-like "bicontinuous polyhedra" (or infinite polyhedra) whose flat walls partition space into a pair of mutually interpenetrating labyrinths. Two bicontinuous polyhedra can be self-assembled: the regular (or Platonic) Petrie-Coxeter infinite polyhedron (denoted {6,4|4}) and the semi-regular Hart "gyrangle". The latter structure is chiral, with both left- and right-handed versions. We show that the Petrie-Coxeter assembly is constructed from two complementary populations of hexagonal nanoplates. Furthermore, we find that the 3D chiral Hart gyrangle can be assembled from identical achiral triangular nanoplates decorated with regioselective complementary interaction sites. The assembled Petrie-Coxeter and Hart polyhedra are faceted versions of two of the simplest triply periodic minimal surfaces, namely, Schwarz's primitive and Schoen's gyroid surfaces, respectively, offering alternative routes to those bicontinuous nanostructures, which are widespread in synthetic and biological materials.
Nature employs an impressive range of topologically complex ordered nanostructures that occur in various forms in both natural and synthetic materials. A particular class of these exhibits negative curvature and forms periodic saddle-shaped surfaces in three dimensions. Unlike pattern formation on flat or positively curved surfaces like spherical systems, the understanding of patterning on such surfaces is highly complicated due to the structures being intrinsically intertwined in three dimensions. We present a new method for visualisation and analysis of patterns on triply periodic negatively curved surfaces by mapping to two-dimensional hyperbolic space analogous to spherical projections in cartography thus effectively creating a more accessible "hyperbolic map" of the pattern. Specifically, we exemplify the method via the simplest triply periodic minimal surfaces: the Primitive, Diamond, and Gyroid in their universal cover along with decorations from a soft materials, whose structures involve decorations of soft matter on negatively curved surfaces, not necessarily minimal.
Symmetric, elegantly entangled structures are a curious mathematical construction that has found their way into the heart of the chemistry lab and the toolbox of constructive geometry. Of particular interest are those structures-knots, links and weavings-which are composed locally of simple twisted strands and are globally symmetric. This paper considers the symmetric tangling of multiple 2-periodic honeycomb networks. We do this using a constructive methodology borrowing elements of graph theory, low-dimensional topology and geometry. The result is a wide-ranging enumeration of symmetric tangled honeycomb networks, providing a foundation for their exploration in both the chemistry lab and the geometers toolbox.
The comprehension of form generally assumes a euclidean three-dimensional perspective. I argue here that non-euclidean geometry has much to offer in understanding structures of atomic crystals, molecular liquid crystals and related mesoporous inorganic materials and biominerals.
Contemporary scientific research is competitive, costly and coupled to the parallel universe of commerce. A Faustian bargain between scientists and politicians allows the funding to flow. There is another path: to slow down, think and experiment without the pressure of competition and frequent publication. That path will come at a cost: reduced funding for people and equipment. The article compares and contrasts the most creative musical and visual artists with the current scientific model. I suggest that science requires acceptance that true creativity can only come by decoupling from current commercial and political imperatives.
Biomineralization in a starfish displays morphologically complex features
The intrinsic, hyperbolic crystallography of the Diamond and Gyroid minimal surfaces in their conventional unit cells is introduced and analysed. Tables are constructed of symmetry subgroups commensurate with the translational symmetries of the surfaces as well as group-subgroup lattice graphs.
Conventional embeddings of the edge-graphs of Platonic polyhedra, {f,z}, where f,z denote the number of edges in each face and the edge-valence at each vertex, respectively, are untangled in that they can be placed on a sphere (S-2) such that distinct edges do not intersect, analogous to unknotted loops, which allow crossing-free drawings of S-1 on the sphere. The most symmetric (flag-transitive) realizations of those polyhedral graphs are those of the classical Platonic polyhedra, whose symmetries are *2fz, according to Conway's two-dimensional (2D) orbifold notation (equivalent to Schonflies symbols I-h, O-h, and T-d). Tangled Platonic {f,z} polyhedra-which cannot lie on the sphere without edge-crossings-are constructed as windings of helices with three, five, seven,... strands on multigenus surfaces formed by tubifying the edges of conventional Platonic polyhedra, have (chiral) symmetries 2fz (I, O, and T), whose vertices, edges, and faces are symmetrically identical, realized with two flags. The analysis extends to the "theta(z)" polyhedra, {2,z}. The vertices of these symmetric tangled polyhedra overlap with those of the Platonic polyhedra; however, their helicity requires curvilinear (or kinked) edges in all but one case. We show that these 2fz polyhedral tangles are maximally symmetric; more symmetric embeddings are necessarily untangled. On one hand, their topologies are very constrained: They are either self-entangled graphs (analogous to knots) or mutually catenated entangled compound polyhedra (analogous to links). On the other hand, an endless variety of entanglements can be realized for each topology. Simpler examples resemble patterns observed in synthetic organometallic materials and clathrin coats in vivo.
The in-surface crystallography of the family of three-periodic minimal surfaces (TPMS) consisting of the Primitive, Diamond, and Gyroid surfaces has been explored in detail in recent decades [1, 2].We begin by reviewing the underlying group theory and geometry as well as the relationship between the TPMS and their universal covering space, hyperbolic two-space, the fundamentals of which are shown in Figure 1(a).We describe how these methods can be used to tailor the topology and geometry of three-periodic nets realised as embeddings commensurate with the symmetries of these surfaces [3-5] as shown in Figure 1(b).Using these ideas, we demonstrate how a number of nets with pre-specified topological properties are readily produced in this manner and assess their relevance for further study in the context of reticular chemistry and soft matter materials science.
ABSTRACT We develop tools to explore and catalogue the topologies of knotted or pseudoknotted circular folds due to secondary and tertiary interactions within a closed loop of RNA which generate multiple double-helices due (for example) to strand complementarity. The fold topology is captured by a ‘contracted fold’ which merges helices separated by bulges and removes hairpin loops. Contracted folds are either trivial or pseudoknotted. Strand folding is characterised by a rigid-vertex ‘polarised strand graph’, whose vertices correspond to double-helices and edges correspond to strands joining those helices. Each vertex has a plumbline whose polarisation direction defines the helical axis. That polarised graph has a corresponding circular ribbon diagram and canonical alphanumeric fold label. Key features of the ‘fully-flagged’ fold are the arrangement of complementary domains along the strand, described by a numerical bare fold label, and a pair of binary ‘flags’: a parity flag that specifies the twist in each helix (even or odd half-twists), and an orientation flag that characterises each double-helix as parallel or antiparallel. A simple algorithm is presented to translate an arbitrary fold label into a polarised strand graph. Any embedding of the graph in 3-space is an admissible fold geometry; the simplest embeddings minimise the number of edge-crossings in a planar graph drawing. If that number is zero, the fold lies in one of two classes: (a)-type ‘relaxed’ folds, which contain conventional junctions and (b)-type folds whose junctions are described as meso-junctions in H. Wang and N.C. Seeman, Biochem , vol. 34, pp920-929. (c)-type folds induce polarised strand graphs with edge-crossings, regardless of the planar graph drawing. Canonical fold labelling allows us to sort and enumerate all ‘semi-flagged’ folds with up to six contracted double-helices as windings around the edges of a graph-like fold skeleton, whose cyclomatic number - the ‘fold genus’ - ranges from 0 – 3, resulting in a pair of duplexed strands along each skeletal edge. Those semi-flagged folds admit both even and odd double-helical twists. Appending specific parity flags to those semi-flagged folds gives fully-flagged (a)-type folds, which are also enumerated up to genus-3 cases. We focus on all-antiparallel folds, characteristic of conventional ssRNA and enumerate all distinct (a), (b) and (c)-type folds with up to five double-helices. Those circular folds lead to pseudoknotted folds for linear ssRNA strands. We describe all linear folds derived from (a) or (b)-type circular folds with up to four contracted double-helices, whose simplest cases correspond to so-called H , K and L pseudoknotted folds, detected in ssRNA. Fold knotting is explored in detail, via constructions of so-called antifolds and isomorphic folds. We also tabulate fold knottings for (a) and (b)-type folds whose embeddings minimise the number of edge-crossings and outline the procedure for (c)-type folds. The inverse construction - from a specific knot to a suitable nucleotide sequence - results in a hierarchy of knots. A number of specific alternating knots with up to 10 crossings emerge as favoured fold designs for ssRNA, since they are readily constructed as (a)-type all-antiparallel folds.
We enumerate trivalent reticulations of two- and three-periodic hyperbolic surfaces by equal-sided n-gonal faces, (n, 3), where n = 7, 8, 9, 10, 12. These are the simplest hyperbolic generalizations of the planar graphene net, (6, 3) and dodecahedrane, (5, 3). The enumeration proceeds by deleting isometries of regular reticulations of two-dimensional hyperbolic space until the (n, 3) nets can be embedded in euclidean three-space via periodic hyperbolic surfaces. Those nets are then symmetrized in euclidean space retaining their net topology, leading to explicit crystallographic net embeddings whose edges are as equal as possible, affording candidtae patterns for graphitic schwarzites. The resulting schwarzites are the most symmetric examples. More than one hundred topologically distinct nets are described, most of which are novel.
We investigated the structures of normal (type I) bicontinuous cubic phases in hexa-, hepta-, and octaethylene glycol dodecyl ether/water mixtures by small-angle X-ray crystallography of single-crystal domains. Reconstructed electron densities showed that the hydrophilic chains with high electron density are confined to a film centered on the surface of the Gyroid (a triply periodic minimal surface), while hydrophobic chains with low electron density are distributed within the pair of interwoven labyrinths carved out by the Gyroid. Further, the local minimum within the high electron density region, due to bulk water, coincides precisely with the Gyroid. This minimum is less pronounced in mixtures with longer ethylene glycol chains, consistent with their decreased water content. Our analysis clearly shows that the polar-nonpolar interfaces are parallel to the Gyroid surface in all mixtures. The repulsive hydration or overlapping force between the pair of facing monolayers of ethylene glycol chains on either side of the Gyroid surface is the likely origin of the parallel interfaces.
This communication briefly reviews why network topology is an important tool (for understanding, comparing, communicating, designing, and solving crystal structures from powder diffraction data) and then discusses the terms of an IUPAC project dealing with various aspects of network topology. One is the ambiguity in node assignment, and this question is addressed in more detail. First, we define the most important approaches: the “all node” deconstruction considering all branch points of the linkers, the “single node” deconstruction considering only components mixed, and the ToposPro “standard representation” also considering linkers as one node but, if present, takes each metal atom as a separate node. These methods are applied to a number of metal–organic framework structures (MOFs, although this is just one example of materials this method is applicable on), and it is concluded that the “all node” method potentially yields more information on the structure in question but cannot be recommended as the o...
We analyse two-component "weavings" made of a pair of dual (p,q) and (q,p) nets that undulate on both sides of the sphere, the plane and the hyperbolic plane. Families of weavings are described, sharing a common parent net. The examples describe zero-, two- and three-periodic weavings in three-space. We derive all edge-2-transitive weavings with (p,q)=(3,3), (4,3), (4,4), (4,6) using Delaney-Dress tiling theory, described in detail. The two-dimensional hyperbolic weavings are mapped into (euclidean) three-space to form a pair of catenated crystalline nets. The examples suggest generalisations to other weavings on surfaces, including weavings of filaments. A simple hyperbolic weavings of filaments is derived, analogous to the common warp-and-weft filament weaving in the plane. The resulting three-periodic pattern is related to the molecular-scale weaving in the synthetic COF-505 material synthesized by Liu et al. [Science, vol. 351: 365-369, 2016].
This paper describes an invariant representation for finite graphs embedded on orientable tori of arbitrary genus, with working examples of embeddings of the Möbius-Kantor graph on the torus, the genus-2 bitorus and the genus-3 tritorus, as well as the two-dimensional, 7-valent Klein graph on the tritorus (and its dual: the 3-valent Klein graph). The genus-2 and -3 embeddings describe quotient graphs of 2- and 3-periodic reticulations of hyperbolic surfaces. This invariant is used to identify infinite nets related to the Möbius-Kantor and 7-valent Klein graphs.
Significance The simplest 2D regular honeycombs are familiar patterns, found in an extraordinary range of natural and designed systems. They include tessellations of the plane by squares, hexagons, and equilateral triangles. Regular triangular honeycombs also form on the sphere; they are the triangular Platonic polyhedra: the tetrahedron, octahedron, and icosahedron. Regular hyperbolic honeycombs adopt an infinite variety of topologies; these must be distorted to be situated in 3D space and are thus frustrated. We construct minimally frustrated realizations of the simplest hyperbolic honeycombs.
We investigated two distinct lyotropic liquid crystal inverse bicontinuous cubic phases of phytantriol/water mixtures by small-angle X-ray crystallography of the single-crystal regions. Reconstructed electron density maps revealed hydrophilic head and hydrophobic tail regions of the phytantriol bilayer membranes and water regions. The bilayer membranes are shown to be located on the D and gyroid triply periodic minimal surfaces. To investigate the structures of the polar-nonpolar interfaces, we optimized two models: a parallel surface model and a constant mean curvature surface model. The parallel surface model agreed well with the X-ray data, and the R factors, which show the degree of agreement between those structural models and the data, were less than 0.04. In stark contrast, the constant mean curvature surface model deviated significantly from the data, and the R factors were around 0.15. We therefore conclude that the polar-nonpolar interface of the inverse bicontinuous cubic phase of the phytantriol/water system is close to a parallel surface to a triply periodic minimal surface.