Abstract
The field of supramolecular chemistry focuses on the non-covalent interactions between molecules that give rise to molecular recognition and self-assembly processes. Since most non-covalent interactions are relatively weak and form and break without significant activation barriers, many supramolecular systems are under thermodynamic control. Hence, traditionally, supramolecular chemistry has focused predominantly on systems at equilibrium. However, more recently, self-assembly processes that are governed by kinetics, where the outcome of the assembly process is dictated by the assembly pathway rather than the free energy of the final assembled state, are becoming topical. Within the kinetic regime it is possible to distinguish between systems that reside in a kinetic trap and systems that are far from equilibrium and require a continuous supply of energy to maintain a stationary state. In particular, the latter systems have vast functional potential, as they allow, in principle, for more elaborate structural and functional diversity of self-assembled systems — indeed, life is a prime example of a far-from-equilibrium system. In this Review, we compare the different thermodynamic regimes using some selected examples and discuss some of the challenges that need to be addressed when developing new functional supramolecular systems.
Similar content being viewed by others
References
Pross, A. Toward a general theory of evolution: extending Darwinian theory to inanimate matter. J. Syst. Chem. 2, 1 (2011).
Pascal, R., Pross, A. & Sutherland, J. D. Towards an evolutionary theory of the origin of life based on kinetics and thermodynamics. Open Biol. 3, 130156 (2013).
Pascal, R. & Pross, A. The nature and mathematical basis for material stability in the chemical and biological worlds. J. Syst. Chem. 5, 3 (2014).
Whitesides, G. M. & Ismagilov, R. F. Complexity in chemistry. Science 284, 89–92 (1999).
Newth, D. & Finnigan, J. Emergence and self-organization in chemistry and biology. Aust. J. Chem. 59, 841–848 (2006).
Ludlow, R. F. & Otto, S. Systems chemistry. Chem. Soc. Rev. 37, 101–108 (2008).
Peyralans, J. J. P. & Otto, S. Recent highlights in systems chemistry. Curr. Opin. Chem. Biol. 13, 705–713 (2009).
Von Kiedrowski, G., Otto, S. & Herdewijn, P. Welcome home systems chemists. J. Syst. Chem. 1, 1 (2010).
Nitschke, J. R. Systems chemistry: molecular networks come of age. Nature 462, 736–738 (2009).
Gibb, B. C. Teetering towards chaos and complexity. Nature Chem. 1, 17–18 (2009).
Chichak, K. S. et al. Molecular Borromean rings. Science 304, 1308–1312 (2004).
De Greef, T. F. A. et al. Supramolecular polymerization. Chem. Rev. 109, 5687–5754 (2009).
Li, J., Nowak, P. & Otto, S. Dynamic combinatorial libraries: from exploring molecular recognition to systems chemistry. J. Am. Chem. Soc. 135, 9222–9239 (2013).
Hamieh, S. et al. A “dial-a-receptor” dynamic combinatorial library. Angew. Chem. Int. Ed. 52, 12368–12372 (2013).
Ponnuswamy, N., Cougnon, F. B. L., Clough, J. M., Dan Pantoş, G. & Sanders, J. K. M. Discovery of an organic trefoil knot. Science 338, 783–785 (2012).
Du, G., Moulin, E., Jouault, N., Buhler, E. & Giuseppone, N. Muscle-like supramolecular polymers: integrated motion from thousands of molecular machines. Angew. Chem. Int. Ed. 51, 12504–12508 (2012).
Lasic, D. D. Kinetic and thermodynamic effects on the structure and formation of phosphatidylcholine vesicles. Hepatology 13, 1010–1013 (1991).
Guida, V. Thermodynamics and kinetics of vesicles formation processes. Adv. Colloid Interface Sci. 161, 77–88 (2010).
Tayebi, L., Vashaee, D. & Parikh, A. N. Stability of uni- and multillamellar spherical vesicles. ChemPhysChem 13, 314–322 (2011).
Stano, P. & Luisi, P. L. Achievements and open questions in the self-reproduction of vesicles and synthetic minimal cells. Chem. Commun. 46, 3639–3653 (2010).
Hanczyc, H. H. & Szostak, J. W. Replicating vesicles as models of primitive cell growth and division. Curr. Opin. Chem. Biol. 8, 660–664 (2004).
Zepik, H. H. & Walde, P. Achievements and challenges in generating protocell models. ChemBioChem 9, 2771–2772 (2008).
Loakes, D. & Holliger, P. Darwinian chemistry: towards the synthesis of a simple cell. Mol. BioSyst. 5, 686–694 (2009).
Takahashi, H. et al. Autocatalytic membrane-amplification on a pre-existing vesicular surface. Chem. Commun. 46, 8791–8793 (2010).
Korevaar, P. A. et al. Pathway complexity in supramolecular polymerization. Nature 481, 492–496 (2012).
Ogi, S., Sugiyasu, K., Manna, S., Samitsu, S. & Takeuchi, M. Living supramolecular polymerization realized through a biomimetic approach. Nature Chem. 6, 188–195 (2014).
Tevis, I. D. et al. Self-assembly and orientation of hydrogen-bonded oligothiophene polymorphs at liquid-membrane-liquid interfaces. J. Am. Chem. Soc. 133, 16486–16494 (2011).
Giri, G. et al. Tuning charge transport in solution-sheared organic semiconductors using lattice strain. Nature 480, 504–508 (2011).
Hill, J. P. et al. Self-assembled hexa-peri-hexabenzocoronene graphitic nanotube. Science 304, 1481–1483 (2004).
Würthner, F., Yao, S. & Beginn, U. Highly ordered merocyanine dye assemblies by supramolecular polymerization and hierarchical self-organization. Angew. Chem. Int. Ed. 42, 3247–3250 (2003).
Lohr, A., Lysetska, M. & Würthner, F. Supramolecular stereomutation in kinetic and thermodynamic self-assembly of helical merocyanine dye nanorods. Angew. Chem. Int. Ed. 44, 5071–5074 (2005).
Hirst, A. R. et al. Biocatalytic induction of supramolecular order. Nature Chem. 2, 1089–1094 (2010).
Wang, Q. G. et al. Enzymatic hydrogelation to immobilize an enzyme for high activity and stability. Soft Matter 4, 550–553 (2008).
Boekhoven, J. et al. Catalytic control over supramolecular gel formation. Nature Chem. 5, 433–437 (2013).
Lohr, A. & Würthner, F. Evolution of homochiral helical dye assemblies: involvement of autocatalysis in the “majority-rules” effect. Angew. Chem. Int. Ed. 47, 1232–1236 (2008).
Von Kiedrowski, G. A self-replicating hexadeoxynucleotide. Angew. Chem. Int. Ed. 24, 932–935 (1986).
Tjivikua, T., Ballester, P. & Rebek, J. A self-replicating system. J. Am. Chem. Soc. 112, 1249–1250 (1990).
Lee, D. H., Granja, J. R., Martinez, J. A., Severin, K. & Ghadiri, M. R. A self-replicating peptide. Nature 382, 525–528 (1996).
Rubinov, B. et al. Transient fibril structures facilitating nonenzymatic self-replication. ACS Nano 6, 7893–7901 (2012).
Carnall, J. M. A. et al. Mechanosensitive self-replication driven by self-organization. Science 327, 1502–1506 (2010).
Malakoutikhah, M. et al. Uncovering the selection criteria for the emergence of multi-building-block replicators from dynamic combinatorial libraries. J. Am. Chem. Soc. 135, 18406–18417 (2013).
Schulman, R., Yulke, B. & Winfree, E. Robust self-replication of combinatorial information via crystal growth and scission. Proc. Natl Acad. Sci. USA 109, 6405–6410 (2012).
Fialkowski, M. et al. Principles and implementations of dissipative (dynamic) self-assembly. J. Phys. Chem. B 110, 2482–2496 (2006).
Klajn, R., Bishop, K. J. M. & Grzybowski, B. A. Light-controlled self-assembly of reversible and irreversible nanoparticle suprastructures. Proc. Natl Acad. Sci. USA 104, 10305–10309 (2007).
Boekhoven, J. et al. Dissipative self-assembly of a molecular gelator by using a chemical fuel. Angew. Chem. Int. Ed. 49, 4825–4828 (2010).
Debnath, S., Roy, S. & Ulijn, R. V. Peptide nanofibers with dynamic instability through nonequilibrium biocatalytic assembly. J. Am. Chem. Soc. 135, 16789–16792 (2013).
Emond, M. et al. Energy propagation through a protometabolism leading to the local emergence of singular stationary concentration profiles. Chem. Eur. J. 18, 14375–14383 (2012).
Krabbenborg, S. O. Surface Gradients Under Electrochemical Control Ch. 7, PhD thesis, Univ. Twente (2014).
Kudernac, T. et al. Electrically driven directional motion of a four-wheeled molecule on a metal surface. Nature 479, 208–211 (2011).
Ragazzon, G., Baroncini, M., Silvi, S., Venturi, M. & Credi, A. Light-powered autonomous and directional molecular motion of a dissipative self-assembling system. Nature Nanotech. 10, 70–75 (2015).
Gasparini, G., Dal Molin, M. & Prins, L. J. Dynamic approaches towards catalyst discovery. Eur. J. Org. Chem. 2010, 2429–2440 (2010).
Fanlo-Virgós, H., Roig Alba, A.-N., Hamieh, S., Colomb-Delsuc, M. & Otto, S. Transient substrate-induced catalyst formation in a dynamic molecular network. Angew. Chem. Int. Ed. 53, 11346–11350 (2014).
Nguyen, R., Allouche, L., Buhler, E. & Giuseppone, N. Dynamic combinatorial evolution within self-replicating supramolecular assemblies. Angew. Chem. Int. Ed. 48, 1093–1096 (2009).
Del Amo, V. & Philp, D. Integrating replication-based selection strategies in dynamic covalent systems. Chem. Eur. J. 16, 13304–13318 (2010).
de Greef, T. F. A. & Meijer, E. W. Materials science: Supramolecular polymers. Nature 453, 171–173 (2008).
Klajn, R., Wesson, P. J., Bishop, K. J. M. & Grzybowski, B. A. Writing self-erasing images using metastable nanoparticle “inks”. Angew. Chem. Int. Ed. 48, 7035–7039 (2009).
Acknowledgements
This work was supported by the NWO, the ERC, COST CM1304 and the Dutch Ministry of Education, Culture and Science (Gravitation Program 024.001.035). The authors wish to express their gratitude to M. Colomb-Delsuc for helping with the graphics in Fig. 4.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Rights and permissions
About this article
Cite this article
Mattia, E., Otto, S. Supramolecular systems chemistry. Nature Nanotech 10, 111–119 (2015). https://doi.org/10.1038/nnano.2014.337
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nnano.2014.337
- Springer Nature Limited
This article is cited by
-
Supramolecular assembly guided by photolytic redox cycling
Nature Synthesis (2023)
-
Synthetically encoded complementary oligomers
Nature Reviews Chemistry (2023)
-
Functional advantages of building nanosystems using multiple molecular components
Nature Chemistry (2023)
-
Autocatalytic flow chemistry
Scientific Reports (2023)
-
Creation of kinetically-controlled supramolecular systems based on coordination chemistry
Journal of Inclusion Phenomena and Macrocyclic Chemistry (2023)