Manipulating the monolayer : responsive and reversible control of colloidal inorganic nanoparticle properties

Funding: EPSRC EP/K016342/1; Leverhulme Trust: RPG-2015-042For a wide range of nanomaterials, surface-bound molecules play a central role in defining properties, and are key to integration with other components – be they molecules, surfaces, or other nanoparticles. Predictable and general methods for manipulating the surface monolayer are therefore crucial to exploiting this new region of chemical space. This review highlights limitations of the few established methods for controlling nanoparticle-bound molecular functionality, then focuses on emerging new strategies. In particular, approaches that can achieve stimuli-responsive and reversible modification of surface-bound molecules in colloidal solution are examined, with an emphasis on using these methods to control nanoparticle properties such as solvent compatibility, catalytic activity and cytotoxicity. Finally, the outstanding challenges and future potential for precisely controlled nanoparticle bound monolayers are discussed.Publisher PDFPeer reviewe

Reversible control of nanoparticle functionalization and physicochemical properties by dynamic covalent exchange

This work was supported by the EPSRC (EP/K016342/1 and DTG), the University of St Andrews, and by a Royal Society of Edinburgh/Scottish Government Fellowship (E.R.K.).Existing methods for the covalent functionalization of nanoparticles rely on kinetically controlled reactions, and largely lack the sophistication of the preeminent oligonucleotide-based noncovalent strategies. Here we report the application of dynamic covalent chemistry for the reversible modification of nanoparticle (NP) surface functionality, combining the benefits of non-biomolecular covalent chemistry with the favorable features of equilibrium processes. A homogeneous monolayer of nanoparticle-bound hydrazones can undergo quantitative dynamic covalent exchange. The pseudomolecular nature of the NP system allows for the in situ characterization of surface-bound species, and real-time tracking of the exchange reactions. Furthermore, dynamic covalent exchange offers a simple approach for reversibly switching—and subtly tuning—NP properties such as solvophilicity.Publisher PDFPeer reviewe