Supramolecular chemistry promises the assembly of molecular units into well-defined architectures, via specific non-covalent interactions. Nanoparticles (NPs) possess unique size-dependent properties that are not observable in bulk materials. The combination of both fields is attractive, since stable, yet reversible hybrid assemblies hold great promise for biomedical applications.Supramolecular nanoparticles (SNPs) are particles in which multiple copies of different building blocks are brought together by specific noncovalent interactions, resulting in assemblies that are typically larger than the building blocks themselves. NP formation based on supramolecular cyclodextrin host-guest interactions has been demonstrated by the groups of Davis [1] and Tseng [2] whereby the size of the formed NPs could be altered by varying the ratio of the monovalent and multivalent guest derivatives. These materials have been used for siRNA delivery and as MRI contrast agents, respectively. Similarly, we have used cucurbit[8]uril ternary complexes in a similar manner to achieve size-controlled nanoparticles.[3,4]At first sight completely unrelated is the area of metal-organic framework (MOF) particles. Also these are actively pursued for biomedical applications. At the same time, these are also constituted of small, multivalent building blocks. The same principle of capping with monovalent ligands has been used by us to achieve size control as well as functionalization in MOF NPs.[5]In the current paper, we will discuss the physicochemical design rules of how the stoichiometry of the building blocks provides size control in both these organic SNPs as well as the MOF NPs. PEG chains of different MWs are attached to both types of particles and their effect on size control are discussed as well.  References1.  M. E. Davis, J. E. Zuckerman, C. H. J. Choi, D. Seligson, A. Tolcher, C. A. Alabi, Y. Yen, J. D. Heidel and A. Ribas, Nature 464 , 1067 (2010).2.  H. Wang, S. Wang, H. Su, K.-J. Chen, A. L. Armijo, W.-Y. Lin, Y. Wang, J. Sun, K.-i. Kamei, J. Czernin, C. G. Radu and H.-R. Tseng, Angew. Chem., Int. Ed. 48 , 4344 (2009).3.  C. Stoffelen and J. Huskens, Chem. Commun. 49 , 6740 (2013).4.  C. Stoffelen, J. Voskuhl, P. Jonkheijm and J. Huskens, Angew. Chem. Int. Ed, in press (2014).5.  T. Rijnaarts, R. Mejia-Ariza, R. J. M. Egberink and J. Huskens, submitted.

Supramolecular strategies for the control of size and functionalization of organic and metal-organic framework nanoparticles

248th National Meeting (2014)

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