» Articles » PMID: 24557132

Living Supramolecular Polymerization Realized Through a Biomimetic Approach

Overview
Journal Nat Chem
Specialty Chemistry
Date 2014 Feb 22
PMID 24557132
Citations 135
Authors
Affiliations
Soon will be listed here.
Abstract

Various conventional reactions in polymer chemistry have been translated to the supramolecular domain, yet it has remained challenging to devise living supramolecular polymerization. To achieve this, self-organization occurring far from thermodynamic equilibrium--ubiquitously observed in nature--must take place. Prion infection is one example that can be observed in biological systems. Here, we present an 'artificial infection' process in which porphyrin-based monomers assemble into nanoparticles, and are then converted into nanofibres in the presence of an aliquot of the nanofibre, which acts as a 'pathogen'. We have investigated the assembly phenomenon using isodesmic and cooperative models and found that it occurs through a delicate interplay of these two aggregation pathways. Using this understanding of the mechanism taking place, we have designed a living supramolecular polymerization of the porphyrin-based monomers. Despite the fact that the polymerization is non-covalent, the reaction kinetics are analogous to that of conventional chain growth polymerization, and the supramolecular polymers were synthesized with controlled length and narrow polydispersity.

Citing Articles

Heterogeneously catalyzed supramolecular polymerization: essential roles of nucleation and fragmentation-induced autocatalysis in chiral transfer.

Shi P, Chen G, Chen Q, Wu H, Li S, Cao X Chem Sci. 2025; .

PMID: 40018663 PMC: 11862829. DOI: 10.1039/d4sc07894b.


Consecutive Complex Aggregation Pathway in Covalent Helical Polymer-Metal Complexes: Nanospheres with Controlled P/M Macroscopic Chirality.

Tarrio J, Hermida B, Rodriguez R, Crassous J, Quinoa E, Freire F Small. 2025; 21(7):e2409379.

PMID: 39973346 PMC: 11840455. DOI: 10.1002/smll.202409379.


A coopetition-driven strategy of parallel/perpendicular aromatic stacking enabling metastable supramolecular polymerization.

Gao Z, Xie X, Zhang J, Yuan W, Yan H, Tian W Nat Commun. 2024; 15(1):10762.

PMID: 39737958 PMC: 11686131. DOI: 10.1038/s41467-024-55106-z.


Secondary nucleation guided noncovalent synthesis of dendritic homochiral superstructures via growth on and from surface.

Pramatha S, Srideep D, Pattnaik U, Sahu R, Suresh D, Yadav A Nat Commun. 2024; 15(1):10808.

PMID: 39737948 PMC: 11685712. DOI: 10.1038/s41467-024-55107-y.


Modulating self-assembly and polymorph transitions in bisdendronized squaramides.

Bujosa S, Rubert L, Rotger C, Soberats B Commun Chem. 2024; 7(1):296.

PMID: 39695275 PMC: 11655634. DOI: 10.1038/s42004-024-01391-0.


References
1.
Korevaar P, George S, Markvoort A, Smulders M, Hilbers P, Schenning A . Pathway complexity in supramolecular polymerization. Nature. 2012; 481(7382):492-6. DOI: 10.1038/nature10720. View

2.
Shao C, Stolte M, Wurthner F . Quadruple π stack of two perylene bisimide tweezers: a bimolecular complex with kinetic stability. Angew Chem Int Ed Engl. 2013; 52(29):7482-6. DOI: 10.1002/anie.201302479. View

3.
Chen Z, Lohr A, Saha-Moller C, Wurthner F . Self-assembled pi-stacks of functional dyes in solution: structural and thermodynamic features. Chem Soc Rev. 2009; 38(2):564-84. DOI: 10.1039/b809359h. View

4.
Aguzzi A, Calella A . Prions: protein aggregation and infectious diseases. Physiol Rev. 2009; 89(4):1105-52. DOI: 10.1152/physrev.00006.2009. View

5.
Lohr A, Wurthner F . Evolution of homochiral helical dye assemblies: involvement of autocatalysis in the "majority-rules" effect. Angew Chem Int Ed Engl. 2008; 47(7):1232-6. DOI: 10.1002/anie.200704550. View