Pathway complexity in supramolecular polymerization

P.A. Korevaar, S.J. George, A.J. Markvoort, M.M.J. Smulders, P.A.J. Hilbers, A.P.H.J. Schenning, T.F.A. Greef, de, E.W. Meijer

Research output: Contribution to journalArticleAcademicpeer-review

381 Citations (Scopus)

Abstract

Self-assembly provides an attractive route to functional organic materials, with properties and hence performance depending sensitively on the organization of the molecular building blocks1, 2, 3, 4, 5. Molecular organization is a direct consequence of the pathways involved in the supramolecular assembly process, which is more amenable to detailed study when using one-dimensional systems. In the case of protein fibrils, formation and growth have been attributed to complex aggregation pathways6, 7, 8 that go beyond traditional concepts of homogeneous9, 10, 11 and secondary12, 13, 14 nucleation events. The self-assembly of synthetic supramolecular polymers has also been studied and even modulated15, 16, 17, 18, but our quantitative understanding of the processes involved remains limited. Here we report time-resolved observations of the formation of supramolecular polymers from p-conjugated oligomers. Our kinetic experiments show the presence of a kinetically favoured metastable assembly that forms quickly but then transforms into the thermodynamically favoured form. Quantitative insight into the kinetic experiments was obtained from kinetic model calculations, which revealed two parallel and competing pathways leading to assemblies with opposite helicity. These insights prompt us to use a chiral tartaric acid as an auxiliary to change the thermodynamic preference of the assembly process19. We find that we can force aggregation completely down the kinetically favoured pathway so that, on removal of the auxiliary, we obtain only metastable assemblies.
LanguageEnglish
Pages492-496
JournalNature
Volume481
Issue number7382
DOIs
StatePublished - 2012

Fingerprint

Polymerization
Self assembly
Kinetics
Polymers
Agglomeration
Oligomers
Nucleation
Experiments
Thermodynamics
Proteins

Cite this

@article{8476ca4019b549eeb78d21188ed315f0,
title = "Pathway complexity in supramolecular polymerization",
abstract = "Self-assembly provides an attractive route to functional organic materials, with properties and hence performance depending sensitively on the organization of the molecular building blocks1, 2, 3, 4, 5. Molecular organization is a direct consequence of the pathways involved in the supramolecular assembly process, which is more amenable to detailed study when using one-dimensional systems. In the case of protein fibrils, formation and growth have been attributed to complex aggregation pathways6, 7, 8 that go beyond traditional concepts of homogeneous9, 10, 11 and secondary12, 13, 14 nucleation events. The self-assembly of synthetic supramolecular polymers has also been studied and even modulated15, 16, 17, 18, but our quantitative understanding of the processes involved remains limited. Here we report time-resolved observations of the formation of supramolecular polymers from p-conjugated oligomers. Our kinetic experiments show the presence of a kinetically favoured metastable assembly that forms quickly but then transforms into the thermodynamically favoured form. Quantitative insight into the kinetic experiments was obtained from kinetic model calculations, which revealed two parallel and competing pathways leading to assemblies with opposite helicity. These insights prompt us to use a chiral tartaric acid as an auxiliary to change the thermodynamic preference of the assembly process19. We find that we can force aggregation completely down the kinetically favoured pathway so that, on removal of the auxiliary, we obtain only metastable assemblies.",
author = "P.A. Korevaar and S.J. George and A.J. Markvoort and M.M.J. Smulders and P.A.J. Hilbers and A.P.H.J. Schenning and {Greef, de}, T.F.A. and E.W. Meijer",
year = "2012",
doi = "10.1038/nature10720",
language = "English",
volume = "481",
pages = "492--496",
journal = "Nature",
issn = "0028-0836",
publisher = "Nature Publishing Group",
number = "7382",

}

Pathway complexity in supramolecular polymerization. / Korevaar, P.A.; George, S.J.; Markvoort, A.J.; Smulders, M.M.J.; Hilbers, P.A.J.; Schenning, A.P.H.J.; Greef, de, T.F.A.; Meijer, E.W.

In: Nature, Vol. 481, No. 7382, 2012, p. 492-496.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Pathway complexity in supramolecular polymerization

AU - Korevaar,P.A.

AU - George,S.J.

AU - Markvoort,A.J.

AU - Smulders,M.M.J.

AU - Hilbers,P.A.J.

AU - Schenning,A.P.H.J.

AU - Greef, de,T.F.A.

AU - Meijer,E.W.

PY - 2012

Y1 - 2012

N2 - Self-assembly provides an attractive route to functional organic materials, with properties and hence performance depending sensitively on the organization of the molecular building blocks1, 2, 3, 4, 5. Molecular organization is a direct consequence of the pathways involved in the supramolecular assembly process, which is more amenable to detailed study when using one-dimensional systems. In the case of protein fibrils, formation and growth have been attributed to complex aggregation pathways6, 7, 8 that go beyond traditional concepts of homogeneous9, 10, 11 and secondary12, 13, 14 nucleation events. The self-assembly of synthetic supramolecular polymers has also been studied and even modulated15, 16, 17, 18, but our quantitative understanding of the processes involved remains limited. Here we report time-resolved observations of the formation of supramolecular polymers from p-conjugated oligomers. Our kinetic experiments show the presence of a kinetically favoured metastable assembly that forms quickly but then transforms into the thermodynamically favoured form. Quantitative insight into the kinetic experiments was obtained from kinetic model calculations, which revealed two parallel and competing pathways leading to assemblies with opposite helicity. These insights prompt us to use a chiral tartaric acid as an auxiliary to change the thermodynamic preference of the assembly process19. We find that we can force aggregation completely down the kinetically favoured pathway so that, on removal of the auxiliary, we obtain only metastable assemblies.

AB - Self-assembly provides an attractive route to functional organic materials, with properties and hence performance depending sensitively on the organization of the molecular building blocks1, 2, 3, 4, 5. Molecular organization is a direct consequence of the pathways involved in the supramolecular assembly process, which is more amenable to detailed study when using one-dimensional systems. In the case of protein fibrils, formation and growth have been attributed to complex aggregation pathways6, 7, 8 that go beyond traditional concepts of homogeneous9, 10, 11 and secondary12, 13, 14 nucleation events. The self-assembly of synthetic supramolecular polymers has also been studied and even modulated15, 16, 17, 18, but our quantitative understanding of the processes involved remains limited. Here we report time-resolved observations of the formation of supramolecular polymers from p-conjugated oligomers. Our kinetic experiments show the presence of a kinetically favoured metastable assembly that forms quickly but then transforms into the thermodynamically favoured form. Quantitative insight into the kinetic experiments was obtained from kinetic model calculations, which revealed two parallel and competing pathways leading to assemblies with opposite helicity. These insights prompt us to use a chiral tartaric acid as an auxiliary to change the thermodynamic preference of the assembly process19. We find that we can force aggregation completely down the kinetically favoured pathway so that, on removal of the auxiliary, we obtain only metastable assemblies.

U2 - 10.1038/nature10720

DO - 10.1038/nature10720

M3 - Article

VL - 481

SP - 492

EP - 496

JO - Nature

T2 - Nature

JF - Nature

SN - 0028-0836

IS - 7382

ER -

Korevaar PA, George SJ, Markvoort AJ, Smulders MMJ, Hilbers PAJ, Schenning APHJ et al. Pathway complexity in supramolecular polymerization. Nature. 2012;481(7382):492-496. Available from, DOI: 10.1038/nature10720