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Protein-macrocycle framework engineering: supramolecular copolymerisation with two disparate calixarenes
Supramolecular Chemistry  (IF1.688),  Pub Date : 2021-06-06, DOI: 10.1080/10610278.2021.1935946
Niamh M. Mockler, Sylvain Engilberge, Martin L Rennie, Colin L Raston, Peter B. Crowley


Water soluble calixarenes are versatile mediators of protein assembly, including the fabrication of crystalline frameworks. Here, we report the X-ray crystal structure of cytochrome c (cytc) co-crystallised with two different calixarenes: phosphonato-calix[6]arene (pclx6) and sulfonato-calix[8]arene (sclx8). Each calixarene type acts as an independent molecular glue that mediates cytc dimers within the crystal. The calixarene-mediated dimers combine to yield chains of cytc-sclx8-cytc-pclx6-pclx6 repeating units. These supramolecular copolymer units pack together, via a protein-protein interface, to yield a porous dendrite-like assembly. Interestingly, the tri-component framework has features in common with previously reported structures of cytc in complex with pclx6 or sclx8. Known protein-calixarene ‘building blocks’ combine in novel ways to yield the tri-component assembly, highlighting the versatility of calixarene molecular glues in protein crystal engineering.