Self-assembled Macrocycles: Design Strategies and Emerging Functions

Talukdar, Dhrubajyoti; Kumar, Jinti Moni; Gole, Bappaditya

doi:10.1021/acs.cgd.3c00677

Cited by 3 publications

(4 citation statements)

References 174 publications

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“…Cucurbit[7]uril clusters and dimeric or trimeric stacks of tetra(4-sulfonatophenyl)porphyrin have also been reported in protein cocrystals. Together, these observations suggest that macrocycle oligomerization , can direct protein assembly. Here, it is insightful to compare with protein–foldamer assemblies.…”

Section: Discussionmentioning

confidence: 99%

Supramolecular Synthons in Protein–Ligand Frameworks

Flood,

Mockler,

Thureau

et al. 2024

Crystal Growth & Design

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Supramolecular synthons, defined as reproducible intermolecular structural units, have greatly aided small molecule crystal engineering. In this paper, we propose that supramolecular synthons guide ligand-mediated protein crystallization. The protein RSL and the macrocycle sulfonato-calix[8]arene cocrystallize in at least four ways. One of these cocrystals is a highly porous cube comprising protein nodes connected by calixarene dimers. We show that mutating an aspartic acid to an asparagine results in two new cubic assemblies that depend also on the crystallization method. One of the new cubic arrangements is mediated by calixarene trimers and has a ∼30% increased cell volume relative to the original crystal with calixarene dimers. Crystals of the sulfonato-calix[8]arene sodium salt were obtained from buffered conditions similar to those used to grow the protein−calix[8]arene cocrystals. X-ray analysis reveals a coordination polymer of the anionic calix[8]arene and sodium cation in which the macrocycle is arranged as staggered stacks of the pleated loop conformation. Remarkably, the calixarene packing arrangement is the same in the simple salt as in the protein cocrystal. With the pleated loop conformation, the calixarene presents an extended surface for binding other calixarenes (oligomerization) as well as binding to a protein patch (biomolecular complexation). Small-angle X-ray scattering data suggest pH-dependent calixarene assembly in solution. Therefore, the calix[8]arene−calix[8]arene structural unit may be regarded as a supramolecular synthon that directs at least two types of protein assembly, suggesting applications in protein crystal engineering.

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Section: Discussionmentioning

confidence: 99%

Supramolecular Synthons in Protein–Ligand Frameworks

Flood,

Mockler,

Thureau

et al. 2024

Crystal Growth & Design

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“…Large macrocycles that self-assemble into extended nanotubular structures provide a fertile middle ground in between molecules and materials. [1][2][3][4][5] As molecules, macrocycles offer processability along with the ability to tune chemical structure with atomic precision. As materials, they possess multifunctional pore channels that can be used to mimic biological water channels, 6 selectively transport molecules, 7,8 conduct ions, [9][10][11][12] and host chemical reactions.…”

Section: Introductionmentioning

confidence: 99%

Controlling the crystal packing and morphology of metal–organic macrocycles through side-chain modification

Zasada,

Le,

Hill

et al. 2024

Preprint

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Supramolecular nanotubes constructed from the self-assembly of conjugated metal–organic macrocycles provide a unique collection of materials properties, including solution processability, porosity, and electrical conductivity. Here we show how small modifications to the macrocycle periphery subtly alter the noncovalent interactions governing self-assembly, leading to large changes in crystal packing, crystal morphology, and materials properties. Specifically, we synthesized five distinct copper-based macrocycles that differ in either the steric bulk, polarity, or hydrogen-bonding ability of the peripheral side-chains. We show that increased steric bulk leads to more disordered π–π stacking and lower electrical conductivity, whereas hydrogen-bonding groups lead to more ordered intermolecular interactions and a dramatic increase in crystallite size. Together, these results establish side-chain engineering as a rich toolkit for controlling the packing structure, particle morphology, and bulk properties of conjugated metal–organic macrocycles.

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“…Secondly, functional groups are involved in one or more intermolecular H-bonding to provide directionality and the required strength to the self-assembled structure. 16 On the contrary, much less attention was paid to exploring the possibility of using nonplanar macrocycles without any directional noncovalent interaction to obtain a well-defined nanostructure. 17 Primarily, unpredictable aggregation and, consequently, undefined nanostructures have been the challenge against using such systems.…”

mentioning

confidence: 99%

“…Secondly, functional groups are involved in one or more intermolecular H-bonding to provide directionality and the required strength to the self-assembled structure. 16…”

mentioning

confidence: 99%