Twisted rectangular subunits self-assemble into a ferritin-like capsule

•Twisted rectangular subcomponents self-assemble into a large tetrahedral architecture•Each triangular face of the tetrahedron is composed three ligand units•A smaller M8L6 cubic assembly forms as an isolable kinetic intermediate•The host binds multiple equivalents dianionic guest Molecular capsules can catalyze reactions, perform chiral separations, and stabilize reactive molecules. Many molecular used for such applications have Platonic geometries—tetrahedral, cubic, octahedral—with single ligands defining edges or faces polyhedron. This limits volume interior cavity thus size substrates that be sequestered, stabilized, transformed. Here, we report metal-organic capsule from simple subcomponents. Instead spanning its vertices, each paneled by ligands, leading to much larger framework than would otherwise observed. The resulting remains enclosed, structure exhibits binding. principles developed herein provide promising platform preparation other architectures with large, enclosed internal volumes. vertices polyhedral protein are spanned capsule-forming subunits, enclosing more cargoes if proteins connected directly. Application cage design synthetic analogs allow given enclose greater volume. self-assembly tetramine subcomponent capsule, panels. 31.8 Å in length—double distance subcomponent. rules followed this system programmed tetramine—it twists out planarity lowest-energy configuration, favoring over simpler cube-like architecture. Unlike capsules, new was observed bind guests. High-symmetry capsules1Aumiller W.M. Uchida M. Douglas T. Protein across length scales.Chem. Soc. Rev. 2018; 47: 3433-3469https://doi.org/10.1039/C7CS00818JCrossref PubMed Google Scholar serve transport store payloads, fragile genetic material viruses, iron within ferritins. these subunits.2Prasad B.V.V. Hardy M.E. 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Solution-state data were consistent Electrospray ionization-mass spectrometry (ESI-MS) composition 2C), 1H diffusion-ordered spectroscopy (DOSY) indicated species solution 2B S21), solvodynamic radius 2.5 nm. expected structure, NMR spectrum 2B, S12, S13) indicates arms magnetically distinct. Two-dimensional spectra S16–S20) enabled assignment signals arm. At lower concentration 2.4 mM shorter reaction time day, 3 isolated 3) instead [Zn8L6]16+ architecture, eight 3). Of 3, handedness ?, alternating give rise Th S47, S48). Mass S10 S11) S1–S9) gave results 3. Either obtained blocks, depending time. Even dilute (158 ?M) solutions slowly converted heating at 70°C months S39), however. infer thermodynamically favored product even concentrations, being product. 2, architecture units. Within mean Zn…Zn ± 0.2 Å, whereas corners 14.2 Å. calculated 5,340 852 Å3, respectively, VOIDOO program.35Kleywegt G.J. Jones T.A. Detection, delineation, measurement display macromolecular structures.Acta Crystallogr. D 1994; 50: 178-185https://doi.org/10.1107/S0907444993011333Crossref (968) Given twice many components almost order magnitude there strong enthalpic driving force overcome likely entropic penalty. biphenyl core tetra-aniline conformational flexibility. requires all bidentate sites lie plane, dihedral angle 5.8° 2.5° phenyl rings central unit wider torsion 30.2° 5.4° avoids penalty associated eclipsing hydrogen atoms Two drive elucidated considering First, preference adopt accommodated suppressed Second, may introduce cuboidal pair junction long one short another. extended brings together only around 14.6 similar Pairs match (mean distance: 10.2 0.1 Å) bridge 15.5 Å). configuration result diminished first principle, conformation, appears play essential role 2: Rectangular ability, thermodynamic preference, been architectures.29Jiao Scholar,31Yang screening series prospective (Section S2.3) revealed bound (hexamolybdate, 4A). progressive addition (nBu4N)2Mo6O19 led appearance signals. After 6 equiv (nBu4N)2Mo6O19, simplified having number original sample shifted chemical shift values S30). DOSY had diffusion coefficient S37), further hypothesis host-guest opposed rearrangement. Å3 enough Mo6O192?, van der Waals 299 BIOVIA Discovery Studio Visualizer.37Discovery Visualizer v21.1.0.20298, Copyright 2020 Dassault Systèmes Biovia Corp.Google below hexamolybdate 4B), complex due differing numbers bound. spectral complexity precluded quantification affinities adducts simplification after convergence species, 5 hexamolybdate. Further discussion found Section S2.1. No interaction spectroscopy, however, accelerate conversion S40 S41). subcomponent, residues paneling capsule. process assembles, resembling capsids, ability guests, set apart largest polyhedra.8Sun Scholar,17Pasquale reported generating product, cuboid general use. Future will explore aspect ratio analogous influences tendency structures. Virus capsids show increasing lead members polyhedra.1Aumiller 2Prasad 3Mateu Extension concepts enable enlarged incorporation well M16L12 containing ligands. origins energetic difference calculations, inform future attempts generate become useful currently possible, including oligonucleotides, congeners. Furthermore, replacement atom 3-position could functionalization both inward-facing outward-facing positions, allowing modification properties cavity, degree enclosure, solubility preferences S50).