Insight on the Intracellular Supramolecular Assembly of DTTO: A Peculiar Example of Cell‐Driven Polymorphism

The assembly of supramolecular structures within living systems is an innovative approach for introducing artificial constructs and developing biomaterials capable of influencing and/or regulating the biological responses of living organisms. By integrating chemical, photophysical, morphological, an...

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Published in:Advanced materials (Weinheim) 2023-10, Vol.35 (42), p.e2302756-n/a
Main Authors: Aloisio, Ludovico, Moschetta, Matteo, Boschi, Alex, Fleitas, Ariel García, Zangoli, Mattia, Venturino, Ilaria, Vurro, Vito, Magni, Arianna, Mazzaro, Raffaello, Morandi, Vittorio, Candini, Andrea, D'Andrea, Cosimo, Paternò, Giuseppe Maria, Gazzano, Massimo, Lanzani, Guglielmo, Di Maria, Francesca
Format: Article
Language:English
Subjects:
Assembly
biomaterials
Biomedical materials
Electrical properties
electroactive fibers
Materials science
Morphology
Nucleation
Optical properties
Photoluminescence
Polymorphism
polymorphs
supramolecular assembly
thiophene
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Summary:The assembly of supramolecular structures within living systems is an innovative approach for introducing artificial constructs and developing biomaterials capable of influencing and/or regulating the biological responses of living organisms. By integrating chemical, photophysical, morphological, and structural characterizations, it is shown that the cell‐driven assembly of 2,6‐diphenyl‐3,5‐dimethyl‐dithieno[3,2‐b:2′,3′‐d]thiophene‐4,4‐dioxide (DTTO) molecules into fibers results in the formation of a “biologically assisted” polymorphic form, hence the term bio‐polymorph. Indeed, X‐ray diffraction reveals that cell‐grown DTTO fibers present a unique molecular packing leading to specific morphological, optical, and electrical properties. Monitoring the process of fiber formation in cells with time‐resolved photoluminescence, it is established that cellular machinery is necessary for fiber production and a non‐classical nucleation mechanism for their growth is postulated. These biomaterials may have disruptive applications in the stimulation and sense of living cells, but more crucially, the study of their genesis and properties broadens the understanding of life beyond the native components of cells. Within live cells, DTTO molecules form amorphous spherical clusters which subsequently accumulate, coalesce, and lead to the formation of fibrous crystals interconnecting different cells. Remarkably, cells produce a distinctive crystalline form, that is, a bio‐polymorph, which cannot be replicated outside cells. These fibers offer a new approach for artificially connecting cells and hold the potential for creating/regenerating cellular communication networks.
ISSN:0935-9648
1521-4095
DOI:10.1002/adma.202302756